CN101137715A - Moulding compound comprising polyoxymethylene and zeolite - Google Patents

Abstract

The invention relates to a moulding compound, comprising between 10 and 99.999 wt. % of at least one polyoxymethylene as component (A1) and between 0.001 and 10 wt. %, (in relation to the weight of the component (A1) contained in the moulding compound), of at least one zeolitic material with a pore diameter ranging between 0.3 and 0.5 nm, determined according to the DIN 66134 and DIN 66135 standards. The size of the particles of zeolitic material ranges between 3 and 7 m, determined according to the ISO 13320 standard. The invention also relates to moulded bodies that are produced from said moulding compound.

Description

The moulding compound that contains polyoxymethylene and zeolite

The present invention relates to moulding compound, particularly contain the thermoplastic compounds of polymethanal polymer and zeolitic material.Moulding compound of the present invention also can contain other component, for example thermoplastic polyurethane.The invention further relates to the method for the described moulding compound of preparation.The present invention also relates to the purposes of zeolitic material, discharge to reduce formaldehyde as the component in the moulding compound that contains polyoxymethylene.The present invention especially preferably relates to the moulding compound that contains polyoxymethylene, and wherein the formaldehyde scavenger of Cun Zaiing only comprises zeolitic material.

Polymethanal polymer prepares by the polymerization of formaldehyde or three _ alkane usually, preferably in the presence of appropriate catalyst, carry out (referring to for example R_mpp Chemie-Lexikon[R_mpp ' s chemistry encyclopedia], Georg Thieme Verlag, the 10th edition, 1999, the V volume, 3490 pages and 3406-3407).

EP 0 789 049A1 have described the polymkeric substance that is endowed static resistance, and described polymkeric substance contains (with other) polyacetal, for example polyoxymethylene.These polymkeric substance also contain the inorganic or organic materials of polar adsorptivity.Zeolite is mentioned as inorganic materials, also with other.The preferable particle size of these zeolites is in the scope of 50-500 micron.The composition that does not openly comprise zeolitic material among the embodiment of specification sheets.

US 6,753, and 363B1 has described by had the polyacetal resin composite of fire retardation by P contained compound and basic nitrogen compound combination.Described specification sheets discloses said composition can contain a large amount of additives, for example antioxidant, for example sterically hindered phenol, photostabilizer or thermo-stabilizer.Also disclose a large amount of compounds as stablizer, example wherein is the organic acid metal-salt, the oxyhydroxide of metal, silicate, zeolite, and hydrotalcite.And then, aspect zeolite, many different structure types are disclosed, example is the zeolite of A, x, Y, L or ZSM type.Particularly preferred zeolite content is the 1-10 weight part in polyacetal resin composite, based on the polyacetal meter of 100 weight parts.6,753, among the 363B1, only an embodiment has described the polyacetal resin composite that contains sterically hindered phenol and zeolite (as thermo-stabilizer), and the weight ratio of zeolite and phenol is 14: 1.6,753,363B1 has also described basic nitrogen compound, and it is used in combination with antioxidant especially, is used to suppress the generation of formaldehyde.

EP 0 288 063A2 have described the antimicrobial polymerizable resin, and it contains antibacterial zeolite particles.Part or all of interchangeable ion in this zeolite replaces by ammonium ion or by antibacterial metal ions, and metal ion is for example silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium.According to the example of EP 0 288 063A2, use the antibacterial zeolite particles of 1 weight part in the resin of per 100 weight parts.

EP 1 264 858A1 have described polyacetal resin composite, and it has high thermostability and low-down burst size of methanal.This low burst size of methanal is by using by polyacetal resin, sterically hindered phenol, photostabilizer and containing the incompatible realization of particular group that the spiro-compounds of triazine ring forms.Composition according to EP 1 264858A1 also can contain thermo-stabilizer.With a large amount of thermo-stabilizers that may use, described zeolite and for example had A, X, Y, L or ZSM type structure.

Similar to EP 1 264 858A1, US 2004/0010064A1 also discloses polyacetal resin composite, wherein thermo-stabilizer for example (with other) contain zeolite.But, openly do not contain the composition of zeolite among the embodiment.

EP 0 789 049A1 disclose the polymkeric substance that is endowed static resistance, it comprises (with thermoplastic structure crosslinked elasticity or thermosetting polymer) polar adsorptivity inorganic materials or polar adsorptivity organic materials, and at least aly have at least 5 carbon atoms and at least 3 heteroatomic polar organic compounds, and the salt of inorganic proton acid.Polar adsorptivity inorganic materials for example is (with other) zeolite.The preferable particle size of polar adsorptivity inorganic materials is in the scope of 50-500 micron.Preferred in addition aspheric particle.Therefore, the sorptive material that uses in the embodiment of EP 0 789 049A1 only comprises fiber.

US 5,710,189 and US 5,847,017 a kind of foaming agent composotion has been described, it contains molecular sieve and foam and forms agent.US 5,710,189 and US 5,847,017 a kind of foamable composition of being made up of resin and foaming agent composotion has also been described.The feature of said composition is to have made up two kinds of molecular sieves that hole dimension is different, and first kind of molecular sieve be used to absorb molecule for example water and ammonia, and second kind of molecular sieve comprises will make resin expanded whipping agent.

In application, need specific thermal characteristics and mechanical property, for example high thermostability, high tenacity, high elastic tensile modulus and/or high yielding stress based on many moulding compounds of polyoxymethylene or moulded product.

Consider the low cost production of moulding compound, the factor of another hope is good nucleation and and then the high crystallization rate of polymethanal polymer composition.

For moulding compound or moulded product in the Foods or drinks field, in the household field, in field of house buildings (especially in inside, house), in the automobile production field (special relevant) or for the suitability in the medical field, the standard of a particularly important is a burst size of methanal with the parts in being installed in automotive interior.Because toxicity, so also wish the burst size of methanal of used moulded product or moulding compound is reduced to minimum degree.According to prior art, this realizes by add special component composition in moulding compound that contains polyoxymethylene or moulded product, and this compound and formaldehyde generation chemical reaction are also removed formaldehyde by the chemical conversion process from moulding compound or moulded product.But these additives can damage polymer properties, and for example machinery and thermostability also can cause decolouring and atomizing.Another shortcoming is to be retained in the system via the product that chemical reaction forms, and also causes above-mentioned infringement easily, maybe must remove from system by the technology of complexity.

So, an object of the present invention is to provide novel moulding compound and moulded product, it has at least a above-mentioned advantageous property.

Another object of the present invention is that novel moulding compound and moulded product are provided especially, and it has can be with the low-down burst size of methanal of plain mode realization.

Another object of the present invention is that a kind of novel moulding compound is provided especially, and it has the low-down burst size of methanal that can realize with plain mode, and has high thermostability simultaneously.

So, the invention provides a kind of moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1) with based at least a zeolitic material of the weight meter 0.001-10 weight % of the component that exists in the moulding compound (A1), the bore dia of described zeolitic material is determined in the scope of 0.3-0.5nm according to DIN66134 and DIN66135, and the particle diameter of wherein said zeolitic material is determined in the scope of 3-7 micron according to ISO 13320.

In the present invention, standard ISO 13320 is 1999-11-01 versions of this standard.The dispersion medium that is used to detect particle diameter comprises deionized water.Used equipment comprises Malvern Mastersizer 2000 (Hydro 2000G assembly).Make that solid content is the sample of 1-2 weight % in water, used magnetic stirrer then 1 minute.Particle diameter is defined as in 50% the size of particle under passing on.

The crystal aluminosilicate that used term " zeolite " expression has orderly channel architecture and orderly cage structure among the present invention.The network of these zeolites is by SiO ₄ ^-And AlO ₄ ^-Tetrahedron is formed, and connects via common bridge joint Sauerstoffatom.The summary of known structure for example is described in M.W.Meier, and D.H.Olson is in Ch.Baerlocher " Atlas of Zeolite Structure Types " the 5th revised edition (Elsevier, London, 2001).Another Groups List can find at URL the Internet address http://topaz.ethz.ch/IZA-SC/SearchRef.htm, has wherein described following structure: ABW especially, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, ETR, EUO, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFR, ISV, ITE, ITH, ITW, IWR, IWW, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NES, NON, NPO, OBW, OFF, OSI, OSO, PAR, PAU, PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG, SFH, SFN, SFO, SGT, SOD, SSY, STF, STI, STT, TER, THO, TON, TSC, UEI, UFI, UOZ, USI, UTL, VET, VFI, VNI, VSV, WEI, WEN, YNU, YUG or ZON.

In order to compensate, in zeolite, find interchangeable positively charged ion owing to Al (III) is introduced the negatron valence state that Si (IV) lattice silicate causes.These cationic object lessons (according to the technology of preparation zeolitic material) are the positively charged ions of sodium, potassium, lithium, rubidium or caesium.Ammonium cation also can be used as positively charged ion and is present in the zeolitic material.If these positively charged ions are replaced by proton, for example via ion-exchange, then product be known as sour form accordingly, be the material of H form.

The bore dia of zeolitic material preferably in the scope of 0.31-0.49nm, more preferably 0.32-0.48nm, more preferably 0.33-0.47nm, more preferably 0.34-0.46nm, preferred especially 0.35-0.45nm.For example, particularly preferred bore dia is 0.36nm, or 0.37nm, or 0.38nm, or 0.39nm, or 0.40nm, or 0.41nm, or 0.42nm, or 0.43nm, or 0.44nm.

So the present invention also provides a kind of above-mentioned moulding compound, wherein the bore dia of zeolitic material is in the scope of 0.37-0.43nm.

The particle diameter of zeolitic material is the 3.1-6.9 micron preferably, more preferably 3.2-6.8 micron, more preferably 3.3-6.7 micron, more preferably 3.4-6.6 micron, more preferably 3.5-6.5 micron, more preferably 3.6-6.4 micron, more preferably 3.7-6.3 micron, more preferably 3.8-6.2 micron, more preferably 3.9-6.1 micron, preferred especially 4.0-6.0 micron.

So the present invention also provides a kind of above-mentioned moulding compound, wherein the particle diameter of zeolitic material is measured according to ISO 13320 in the scope of 4-6 micron.

For example, particularly preferred zeolitic material particle diameter is 4.1 microns, or 4.2 microns, or 4.3 microns, or 4.4 microns, or 4.5 microns, or 4.6 microns, or 4.7 microns, or 4.8 microns, or 4.9 microns, or 5.0 microns, or 5.1 microns, or 5.2 microns, or 5.3 microns, or 5.4 microns, or 5.5 microns, or 5.6 microns, or 5.7 microns, or 5.8 microns, or 5.9 microns.

A particularly preferred embodiment of moulding compound of the present invention comprises such zeolitic material, its bore dia is in the scope of 0.35-0.45nm, more preferably 0.36-0.44nm, more preferably 0.37-0.43nm and wherein particle diameter in the scope of 3.5-6.5 micron, more preferably 3.6-6.4 micron, more preferably 3.7-6.3 micron, more preferably 3.8-6.2 micron, more preferably 3.9-6.1 micron and particularly 4.0-6.0 micron.

So it is that 0.37-0.43nm and particle diameter are the zeolitic material of 4.0-6.0 micron that moulding compound of the present invention very particularly preferably contains bore dia.

In principle, moulding compound of the present invention can contain single kind zeolitic material, or two kinds, three kinds, four kinds or more kinds of mutual different zeolitic materials, as long as at least a zeolitic material has above-mentioned specification about bore dia and particle diameter.In principle, the present invention also comprises such embodiment, wherein moulding compound contains at least two kinds of mutual different zeolitic materials, wherein at least a zeolitic material has above-mentioned specification about bore dia and particle diameter, have different with it bore dias or different with it particle diameters with at least a other zeolitic material, or have different with it bore dias or with different with it particle diameters.

So, the present invention includes such moulding compound, it contains the zeolitic material of particle diameter in the 3-7 micrometer range that at least a bore dia of measuring according to DIN66134 and DIN66135 is measured in the 0.3-0.5nm scope and according to ISO 13320, wherein this moulding compound also contains at least a other different with it zeolitic material, its particle diameter in the 3-7 micrometer range and its bore dia less than 0.3nm or greater than 0.5nm, perhaps its bore dia in the 0.3-0.5nm scope and its particle diameter less than 3 microns or greater than 7 microns, perhaps its bore dia less than 0.3nm or greater than 0.5nm and its particle diameter less than 3 microns or greater than 7 microns.So, a kind of embodiment in back comprises such moulding compound, it contains at least a zeolitic material, measure the bore dia of this zeolitic material according to DIN66134 and DIN66135 and in the 0.3-0.5nm scope and according to ISO 13320, measure the particle diameter of these zeolitic materials in the 3-7 micrometer range, and this moulding compound also contains at least a other zeolitic material, its bore dia less than 0.3nm and its particle diameter less than 3 microns, perhaps its bore dia less than 0.3nm and its particle diameter greater than 7 microns, perhaps its bore dia greater than 0.5nm and its particle diameter less than 3 microns, perhaps its bore dia greater than 0.5nm and its particle diameter greater than 7 microns.

If moulding compound of the present invention contains two or more different zeolitic materials, and the bore dia of every kind of these materials is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135, wherein the particle diameter of zeolitic material is determined in the 3-7 micrometer range according to ISO 13320, then these zeolitic materials can be aspect bore dia different or aspect particle diameter difference, perhaps aspect bore dia with all different aspect the particle diameter.

In a preferred embodiment of moulding compound of the present invention, except bore dia is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135 and particle diameter is determined at least a zeolitic material in the 3-7 micrometer range according to ISO 13320, do not comprise other zeolitic material.

In a particularly preferred embodiment of moulding compound of the present invention, except bore dia is determined in the 0.37-0.43nm scope according to DIN66134 and DIN66135 and particle diameter is determined at least a zeolitic material in the 4-6 micrometer range according to ISO 13320, do not comprise other zeolitic material.

In another preferred embodiment of moulding compound of the present invention, based on the weight meter of the component that exists in moulding compound (A1), described moulding compound contains 0.002-9 weight %, more preferably 0.003-8 weight %, more preferably 0.004-7 weight %, more preferably 0.005-6 weight %, more preferably 0.006-5 weight %, more preferably 0.007-4 weight %, more preferably 0.008-3 weight %, more preferably 0.009-2 weight %, more preferably 0.01-1 weight %, more preferably 0.02-0.9 weight %, more preferably 0.03-0.8 weight %, more preferably 0.04-0.7 weight %, more preferably 0.05-0.6 weight % and the especially preferably zeolitic material of 0.05-0.50 weight %.

So the present invention also provides a kind of above-mentioned moulding compound, it contains the zeolitic material of 0.05-0.50 weight %, based on the weight meter of the component that exists in moulding compound (A1).

In moulding compound of the present invention, weight meter based on the component that in moulding compound, exists (A1), particularly preferred zeolitic material content is 0.05 weight % for example, 0.10 weight %, 0.15 weight %, 0.20 weight %, 0.25 weight %, 0.30 weight %, 0.35 weight %, 0.40 weight %, 0.45 weight % or 0.50 weight %.

A preferred embodiment of moulding compound of the present invention comprises at least a zeolitic material based on the 0.05-0.50 weight % of component in moulding compound (A1) content meter, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and the particle diameter of described zeolitic material is determined in the 3-7 micrometer range according to ISO 13320.

In another preferred embodiment of moulding compound of the present invention, except comprise based on the 0.05-0.50 weight % of component in moulding compound (A1) content meter, bore dia is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and particle diameter is determined at least a zeolitic material in the 3-7 micrometer range according to ISO 13320, does not comprise other zeolitic material.

Another preferred embodiment of moulding compound of the present invention comprises at least a zeolitic material based on the 0.05-0.50 weight % of component in moulding compound (A1) content meter, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.37-0.43nm scope and the particle diameter of described zeolitic material is determined in the 4-6 micrometer range according to ISO 13320.

In the particularly preferred embodiment of moulding compound of the present invention, except comprise based on the 0.05-0.50 weight % of component in moulding compound (A1) content meter, bore dia is according to DIN66134 and DIN66135 is determined in the 0.37-0.43nm scope and particle diameter is determined at least a zeolitic material in the 4-6 micrometer range according to ISO 13320, does not comprise other zeolitic material.

Bore dia is that 0.3-0.5nm scope and particle diameter are the zeolitic material of 3-7 micron, and for example bore dia is that 0.37-0.43nm scope and particle diameter are the preferred zeolite material of 4-6 micron, can have any Si in principle: the Al mol ratio, and according to SiO ₂: Al ₂O ₃Mol ratio calculate.

According to SiO ₂: Al ₂O ₃Mol ratio calculate Si: the Al mol ratio is particularly preferably in being up in 5: 1 the scope.

So the present invention also provides a kind of above-mentioned moulding compound, wherein according to SiO ₂: Al ₂O ₃Mol ratio calculate the Si of described zeolitic material: the Al mol ratio is particularly preferably in being up in 5: 1 the scope.

According to SiO ₂: Al ₂O ₃Mol ratio calculate the Si of described zeolitic material: the Al mol ratio is particularly preferably in 0.9: 1 to 5: 1 the scope, more preferably 0.9: 1 to 4: 1, more preferably 0.9: 1 to 3: 1, more preferably 0.9: 1 to 2: 1 and preferred especially 1: 1 to 2: 1.According to SiO ₂: Al ₂O ₃Mol ratio calculate particularly preferred Si: about in this way 1: 1 of Al molar ratio.

A preferred embodiment of moulding compound of the present invention comprises at least a zeolitic material based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135, its particle diameter is determined in the 3-7 micrometer range and according to SiO according to ISO 13320 ₂: Al ₂O ₃Mol ratio calculate, Si: the Al mol ratio is 0.9: 1 to 5: 1.

In another preferred embodiment of moulding compound of the present invention, except based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia according to DIN66134 and DIN66135 be determined in the 0.3-0.5nm scope, its particle diameter is determined in the 3-7 micrometer range and according to SiO according to ISO 13320 ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio be 0.9: 1 at least a zeolitic material of 5:1, do not comprise other zeolitic material.

Another preferred embodiment of moulding compound of the present invention comprises at least a zeolitic material based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia is determined in the 0.37-0.43nm scope according to DIN66134 and DIN66135, its particle diameter is determined in the 4-6 micrometer range and according to SiO according to ISO 13320 ₂: Al ₂O ₃Mol ratio calculate, Si: the Al mol ratio is 0.9: 1 to 2: 1.

In another preferred embodiment of moulding compound of the present invention, except based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia according to DIN66134 and DIN66135 be determined in the 0.37-0.43nm scope, its particle diameter is determined in the 4-6 micrometer range and according to SiO according to ISO 13320 ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is outside 0.9: 1 to 2: 1 at least a zeolitic material, not comprise other zeolitic material.

Above-mentionedly be determined at the primary crystal size that particle diameter in the 3-7 micrometer range can be represented zeolitic material in principle according to ISO 13320 for the described particle diameter of zeolitic material, or the size of the secondary structure that forms by these primary crystals.So in principle, the primary crystal size of the zeolitic material of measuring by SEM can be different with the particle diameter of measuring according to ISO 13320.

According to a preferred embodiment of the invention, the mean sizes of the primary crystal of zeolitic material is following size, the bore dia of wherein said zeolitic material is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135, its particle diameter be determined in the 3-7 micrometer range according to ISO 13320 and wherein the size of primary crystal detect by SEM.

Its bore dia is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and its particle diameter is determined at the primary crystal mean sizes of the zeolitic material in the 3-7 micrometer range particularly preferably in the highest 3 microns scope according to ISO 13320, more preferably 1.5-3.0 micron, more preferably 1.75-2.75 micron, preferred especially 2.0-2.5 micron detects by SEM in each case.

The length of crystalline diameter and expression crystalline longest edge when these crystal have about parallelepiped shape when used in the present invention term " size of primary crystal " expression is approximately spherical when primary crystal.

Further preferably its bore dia according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and its particle diameter be determined at according to ISO 13320 zeolitic material in the 3-7 micrometer range the primary crystal size at least 90%, more preferably at least 91%, more preferably at least 92%, more preferably at least 93%, more preferably at least 94% and preferred especially at least 95% be in the scope of 1.5-3.0 micron, measure by SEM.

Further preferably its bore dia according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and its particle diameter be determined at according to ISO 13320 zeolitic material in the 3-7 micrometer range the primary crystal size at least 90%, more preferably at least 91%, more preferably at least 92%, more preferably at least 93%, more preferably at least 94% and preferred especially at least 95% be in the scope of 1.75-2.75 micron, measure by SEM.

So the present invention also provides a kind of above-mentioned moulding compound, wherein at least 90% of the primary crystal size of zeolitic material is in the scope of 1.5-3.0 micron, measures by SEM.

A preferred embodiment of moulding compound of the present invention comprises at least a zeolitic material based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135, its particle diameter is determined in the 3-7 micrometer range according to ISO 13320, wherein by SEM measure zeolitic material the primary crystal size at least 90% be in the scope of 1.5-3.0 micron and according to SiO ₂: Al ₂O ₃Mol ratio calculate, Si: the Al mol ratio is 0.9: 1 to 5: 1.

In another preferred embodiment of moulding compound of the present invention, except based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia according to DIN66134 and DIN66135 be determined in the 0.3-0.5nm scope, its particle diameter is determined at the primary crystal size of measuring zeolitic material in the 3-7 micrometer range, by SEM according to ISO 13320 at least 90% is in the scope of 1.5-3.0 micron and according to SiO ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is outside 0.9: 1 to 5: 1 at least a zeolitic material, not comprise other zeolitic material.

Another preferred embodiment of moulding compound of the present invention comprises at least a zeolitic material based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia is determined in the 0.37-0.43nm scope according to DIN66134 and DIN66135, its particle diameter is determined in the 4-6 micrometer range according to ISO 13320, wherein by SEM measure zeolitic material the primary crystal size at least 95% be in the scope of 1.75-2.5 micron and according to SiO ₂: Al ₂O ₃Mol ratio calculate, Si: the Al mol ratio is 0.9: 1 to 2: 1.

In another preferred embodiment of moulding compound of the present invention, except based on the content meter 0.05-0.50 weight % of component in moulding compound (A1), its bore dia according to DIN66134 and DIN66135 be determined in the 0.37-0.43nm scope, its particle diameter is determined at the primary crystal size of measuring zeolitic material in the 4-6 micrometer range, by SEM according to ISO 13320 at least 95% is in the scope of 1.75-2.5 micron and according to SiO ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is outside 0.9: 1 to 2: 1 at least a zeolitic material, not comprise other zeolitic material.

According to a particularly preferred embodiment, the zeolitic material of the existence of at least 75 weight % is not the H form.This content is determined in the 0.3-0.5nm scope based on bore dia according to DIN66134 and DIN66135 especially and particle diameter is determined at zeolitic material in the 3-7 micrometer range according to ISO 13320, if but suitablely also comprise different with it zeolitic materials, as mentioned above.

So the present invention also provides a kind of above-mentioned moulding compound, wherein the zeolitic material of at least 75 weight % is not to exist with the H form.

Further preferably at least 80 weight %, more preferably at least 85 weight %, more preferably at least 90 weight %, more preferably at least 95 weight %, more preferably at least 96 weight % in moulding compound, more preferably at least 97 weight %, more preferably the zeolitic material of at least 98 weight %, preferred especially at least 99 weight % is not to exist with the H form.

So the present invention also provides a kind of above-mentioned moulding compound, wherein the bore dia of zeolitic material is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135 and particle diameter is determined in the 3-7 micrometer range, according to SiO according to ISO 13320 ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is 0.9: 1 to 2: 1, measure by SEM zeolitic material the primary crystal size at least 95% be in the scope of 1.75-2.75 micron, and the described zeolitic material of at least 95 weight % is not to exist with the H form.

Suitable zeolitic material is any material that meets above-mentioned requirements in principle.

The present invention especially preferably has the zeolitic material of the structure that belongs to following type of distributing by X-ray diffraction: BEA, FER, FAU, LTA, MEL, MFI or MOR.Also should be mentioned that the mixed structure of being made up of two or more these types, an example is to have the zeolitic material that mixes the MEL/MFI structure.The zeolitic material of LTA type is particularly preferred.

So, the present invention also provides a kind of above-mentioned moulding compound, its material that comprises the LTA structure type is as zeolitic material, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and particle diameter is determined in the 3-7 micrometer range according to ISO 13320, wherein preferably by SEM measure zeolitic material the primary crystal size at least 95% be in the scope of 1.5-3.0 micron, and/or according to SiO ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is 0.9: 1 to 5: 1.

According to another preferred embodiment of the present invention, above-mentioned zeolitic material has 8-ring passage.Further preferably zeolitic material has 8-ring passage basically.Particularly preferably be, the essentially no 10-of above-mentioned zeolitic material encircles passage and/or does not have 12-ring passage.

So, the present invention also provides a kind of above-mentioned moulding compound, particularly such moulding compound, it contains at least a zeolitic material based on the 0.05-0.50 weight % of component (A1) content meter in the described moulding compound, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and particle diameter is determined in the 3-7 micrometer range according to ISO 13320 and wherein said zeolitic material contains 8-ring passage basically.

Moulding compound of the present invention contains at least a polyoxymethylene as component (A1).

POM-H Acetal homopolymer not only represented in the term of Shi Yonging " polyoxymethylene " in the present invention, and the expression polyacetal copolymer.

So, the present invention also provides a kind of above-mentioned moulding compound, it comprises at least a polyoxymethylene of 10-99.999 weight %, wherein at least a polyoxymethylene is POM-H Acetal homopolymer or at least a polyacetal copolymer at least, or the mixture of being made up of POM-H Acetal homopolymer and at least a polyacetal copolymer at least.

The term of Shi Yonging " POM-H Acetal homopolymer " expression in the present invention only has-CH ₂The unitary polymkeric substance of O-repeated monomer.

The term of Shi Yonging " polyacetal copolymer " expression in the present invention and-CH ₂The O-monomeric unit also has at least one other unitary polymkeric substance, preferably at least one other repeating unit together.These polymkeric substance preferably have at least 50 moles of %'s-CH in main polymer chain ₂The O-repeating unit.

The preferred polyacetal copolymer of the present invention is particularly with-CH ₂The O-monomeric unit also comprises maximum 50 moles of %, more preferably maximum 40 moles of %, more preferably maximum 30 moles of %, more preferably maximum 20 moles of %, more preferably 0.01-20 mole %, more preferably 0.1-10 mole %, more preferably those of following formula repeating unit of 0.2-5 mole %, preferred especially 0.5-3 mole % together:

Radicals R ₁, R ₂, R ₃And R ₄Can be identical or different, be H independently of one another; C ₁-C ₄-alkyl, for example methyl, ethyl, propyl group (for example n-propyl or sec.-propyl) or butyl (for example normal-butyl, isobutyl-or the tertiary butyl); Or halogenated C ₁-C ₄Alkyl, for example halogenated methyl, ethyl, propyl group (for example n-propyl or sec.-propyl) or butyl (for example normal-butyl, isobutyl-or the tertiary butyl), if wherein there are two or more halogenic substituents, then they can be same to each other or different to each other, wherein halogen can for example be F, Cl, Br or I and R wherein ₅Be methylene radical-CH ₂-, carboxaldehyde radicals-CH ₂O-, by C ₁-C ₄-alkyl. or C ₁-C ₄The methylene radical that-haloalkyl replaces is perhaps by C ₁-C ₄-alkyl-or C ₁-C ₄The formaldehyde group that-haloalkyl replaces, wherein if present, on methylene radical and/or carboxaldehyde radicals as substituent C ₁-C ₄-alkyl C ₁-C ₄-haloalkyl can for example be methyl, ethyl, propyl group (for example n-propyl or sec.-propyl) or butyl (for example normal-butyl, isobutyl-or the tertiary butyl), or halogenated methyl, ethyl, propyl group (for example n-propyl or sec.-propyl) or butyl (for example normal-butyl, isobutyl-or the tertiary butyl), if wherein there are two or more halogenic substituents, then they can be same to each other or different to each other and wherein halogen can for example be F, Cl, Br or I.Here, n is 0-3, for example 0,1,2 or 3.

These groups can advantageously be introduced in the multipolymer by the ring-opening reaction of cyclic ethers or cyclopropane carboxaldehyde.Preferred cyclic ethers has following formula

R wherein ₁-R ₅As above define with n.

The example of cyclic ethers of the present invention and cyclopropane carboxaldehyde is an oxyethane, 1,2-propylene oxide, 1,2-butylene oxide ring, 1,3-butylene oxide ring, 1,3-two _ alkane, 1,3-dioxolane and 1,3-dioxepin, and linear oligomer-and polymeric formaldehyde as comonomer, for example poly-dioxolane or poly-dioxepin.Preferred comonomer is C ₂-C ₄Comonomer.

The formaldehyde ter-polymers is another kind of suitable component (A1), can for example react and prepare by one of three _ alkane, above-mentioned cyclic ethers or cyclopropane carboxaldehyde and the 3rd monomer, preferred following formula difunctional compound,

And/or

Wherein Z be chemical bond ,-O-or-OR-.In this respect, R is the alkylidene group that preferably has 1-8 carbon atom, if and suitablely have a suitable substituents, for example methylene radical, ethylidene, propylidene, butylidene, pentylidene, hexylidene, inferior heptyl or octylene, or preferably has the cycloalkylidene of 3-8 carbon atom, if have a suitable substituents with suitable, for example cyclopropylidene, inferior cyclobutyl, cyclopentylidene, cyclohexylidene, inferior suberyl or inferior ring octyl group.

Preferred the type monomer for example is ethylene glycide (ethylene diglycide), diglycidylether, with the diether of forming at 2: 1 according to mol ratio by glycidyl structure division and formaldehyde, two _ alkane or three _ alkane, and has the diether that the aliphatic diol of 2,3,4,5,6,7 or 8 carbon atoms is formed by 2 moles of glycidyl compounds and 1 mole, ethylene glycol, 1 for example, 4-butyleneglycol, 1,3-butyleneglycol, 1,3-cyclobutanediol, 1,2-propylene glycol and 1, the diglycidylether of 4-cyclohexanediol.

The polymethanal polymer of the preferred especially end group stabilizationization of the present invention, its end of the chain has the C-C key.

Preferably 150-200 ℃ of the fusing point of component used according to the invention (A1).(A1) is POM-H Acetal homopolymer as fruit component, and then fusing point is more preferably 170-190 ℃.(A1) is polyacetal copolymer as fruit component, and then fusing point is more preferably 160-180 ℃.These fusing points are temperature of measuring according to ISO 3146 by DSC.

Molar mass (the weight average Mw of component (A1); By the method mensuration of in " embodiment one other experimental technique-molar mass detect ", describing) 11500-240000g/mol ± 10% preferably, and number-average molecular weight Mn 18000-85000 preferably.Further preferably, the molar mass (Mw) of the component of POM-H Acetal homopolymer form (A1) is 11500-240000g/mol ± 10%, and its number-average molecular weight Mn is 35000-85000.Further preferably, the molar mass (Mw) of the component of polyacetal copolymer form (A1) is 80000-220000g/mol ± 10%, and its number-average molecular weight Mn is 18000-38000.The ratio of the Mw of component (A1): Mn is 0.14-12.2g/mol preferably.Further preferably, the ratio of the Mw of the component of POM-H Acetal homopolymer form (A1): Mn is 0.14-6.9g/mol.Further preferably, the Mw of the component of polyacetal copolymer form (A1): Mn is 2.1-12.2g/mol.

Be suitable as the density 1.37-1.45g/cm normally of the polymkeric substance of component (A1) ³, measure according to ISO1183.

So the present invention also provides a kind of above-mentioned moulding compound, wherein the fusing point of component (A1) is 150-200 ℃, measures according to ISO 3146 by DSC.

Particularly, the invention provides a kind of moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1), it is 150-200 ℃ that the fusing point of described component (A1) is measured according to ISO 3146 by DSC, with at least a zeolitic material that contains based on the 0.001-10 weight % of component (A1) weight meter in the described moulding compound, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and particle diameter is determined in the 3-7 micrometer range according to ISO 13320.

Further preferably, the invention provides a kind of moulding compound, its at least a polyoxymethylene that contains 10-99.95 weight % is as component (A1), it is 150-200 ℃ that the fusing point of described component (A1) is measured according to ISO 3146 by DSC, with at least a zeolitic material that contains based on the 0.05-0.5 weight % of component (A1) weight meter in the described moulding compound, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.37-0.43nm scope and particle diameter is determined in the 4-6 micrometer range according to ISO13320.

Further preferably, the invention provides a kind of moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1), it is 150-200 ℃ that the fusing point of described component (A1) is measured according to ISO 3146 by DSC, with at least a zeolitic material that contains based on the 0.05-0.5 weight % of component (A1) weight meter in the described moulding compound, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.37-0.43nm scope and particle diameter is determined in the 4-6 micrometer range according to ISO13320, with at least 90% of the primary crystal size of measuring zeolitic material by SEM be in the scope of 1.5-3.0 micron and according to SiO ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is 0.9: 1 to 5: 1, and described moulding compound does not contain other zeolitic material.

Further preferably, based on the gross weight meter of moulding compound, moulding compound of the present invention contains 15-99.999 weight %, more preferably 20-99.99 weight %, more preferably 25-99.9 weight %, more preferably 30-99 weight %, the more preferably component (A1) of 35-98.5 weight %, preferred especially 40-98 weight %.

Further preferably, based on the gross weight meter of moulding compound, moulding compound of the present invention contains 15-99.999 weight %, more preferably 20-99.99 weight %, more preferably 25-99.9 weight %, more preferably 30-99.7 weight %, the more preferably component (A1) of 35-99.6 weight, preferred especially 40-99.5 weight %.

The example of a special characteristic of polyoxymethylene moulding compositions of the present invention is low-down burst size of methanal.

The burst size of methanal of described moulding compound preferably is at most 8ppm, more preferably is at most 7ppm, more preferably is at most 6ppm, especially preferably is at most 5ppm, measures by VDA275 in each case.For example, the formaldehyde releasing value of moulding compound of the present invention is 2,3,4 or 5ppm.The formaldehyde releasing value of described moulding compound also can be 6,7 or 8ppm.

So the present invention also provides a kind of above-mentioned moulding compound, wherein the formaldehyde releasing value is at most 8ppm, more preferably is at most 7ppm, measures by VDA275.

For the purposes of the present invention, standard VDA275 is in July, 1994 version of this standard.In order to prepare sample, injection moulding machine (Krauss Maffei KM 250 (56)) is used for producing plate from polymeric aggregate.The following selection of injection parameters: screw diameter is 50mm, and bleed type is the Johnson valve nozzle, and nozzle diameter is 4mm, multi-plate mould has 2 spaces, and each space is illustrated in figure 8 as 110*110*2mm, and mould-type is P10/2.0mm, the quality temperature is 200 ℃, mold surface temperature is 90 ℃, and the screw rod speed of rotation is 100rpm, and the screw rod schedule speed is 50mm/s, keep-uping pressure is 50 crust, be 50s cycling time, and wherein pressure hold time is 25s, and be 16s cooling time.Be made up of feed time (1s), pressure hold time (25s), cooling time (16s) and fusion time (5s) cycling time.After injection moulding, it is 40x100mm that injection molding plates is used for preparation size ²Plate, all edges have fresh sawtooth.Also the center in the top edge zone gets out the hole that diameter is 2.5-3mm.So the plate of preparation wore out 24 hours under 23 ℃ and 50% relative humidity under controlled condition before carrying out release experiment.In release experiment, brassboard is at sealable 1L polyethylene bottle internal fixing, and the deionized water of adding 50ml.Sample kept 3 hours in 60 ℃ in air-tight bottle then.Then with bottle in room temperature cooling 60 minutes, and detect formaldehyde content in the distilled water with the flash ranging mode by acetylacetone method.Burst size of methanal represented by ppm, is the form (mg (formaldehyde)/kg sample=ppm) of the formaldehyde content (in deionized water) in every kg dry sample.

Surprisingly, for the purposes of the present invention, this low-down burst size of methanal of discovery polyoxymethylene moulding compositions can be realized by add above-mentioned zeolitic material in component (A1), and the prior art in the polyoxymethylene field only discloses the zeolite that only is used as thermo-stabilizer of other type.For the purpose of prior art, if realize low formaldehyde releasing value, the material of adding always contain can with those of formaldehyde generation chemical reaction, and therefore from moulding compound, remove.But as mentioned above, the use of these formaldehyde scavengers causes in the uncertainty of moulding compound aspect of performance and shortcoming, for example mechanical property and/or thermal characteristics, or the decolouring aspect anti-marquis, or atomizing.

So the feature of the moulding compound of the present invention particularly interpolation of above-mentioned zeolitic material causes low-down burst size of methanal, and do not need the conventional formaldehyde scavenger of prior art.

Can mention with formaldehyde generation chemical reaction and and then the prior art compound from polyoxymethylene moulding compositions, removed normally have the organic compound of at least one uncle and/or secondary amino group, particularly have the organic compound of at least one uncle and/or secondary amino group and particularly have single organic compound that disperses molar mass distribution and have at least one uncle and/or secondary amino group.

The object lesson of the compound of these prior aries is:

(aa) triaizine compounds that replaces of amine, for example contain the triaizine compounds that the amine of at least one aromatic group replaces, for example the compound of following structure:

The radicals R of this structure wherein ₁, R ₂And R ₃Be identical or different, each is hydrogen, halogen atom, hydroxyl, alkyl, alkoxyl group, aryl, alkoxy aryl or replacement or unsubstituted amido naturally, and prerequisite is a radicals R ₁, R ₂And R ₃In at least one be to replace or unsubstituted amido, and radicals R ₁, R ₂And R ₃In at least one by aromatics C ₅-C ₂₀Group is formed, and it can randomly have substituting group.Here, halogen atom is a chlorine or bromine for example, preferred chlorine.Alkyl for example is to have those of 1-6 carbon atom, preferably has 1-4 carbon atom.Alkoxyl group for example is to have those of 1-6 carbon atom, preferably has 1-4 carbon atom.Phenyl, naphthyl and fluorenyl are preferably as aryl, and phenyl alkoxyl group, particularly benzyloxy or phenyl ethoxy are preferably as alkoxy aryl.Substituting group on substituted-amino for example comprises the low alkyl group with 1-6 carbon atom, for example methyl, ethyl, butyl or hexyl; Phenyl; Low-grade alkenyl with 3-6 carbon atom, for example allyl group or hexenyl; Hydroxyalkyl with 1 or 2 carbon atom, for example hydroxymethyl or hydroxyethyl; Cyano group alkyl with 3-6 carbon atom, for example cyano ethyl or cyano group butyl.The triazine with the aromatics replacement that amine replaces for example comprises 2,4-diamino-6-(o, m, p) chloro-phenyl-triazine, 2-amino-4-chloro-6-phenyl triazine, 2-amino-4,6-phenylbenzene triazine, 2,4-diamino-6-naphthyl triazine, 2,4-diamino-6-fluorenyl triazine, 2,4-diamino-6-(o, m, p) alkyl phenyl triazine, wherein methyl is preferably as substituting group, 2,4-diamino-6-(o, m, p) p-methoxy-phenyl triazine and 2,4-diamino-6-(o, m, p) carboxyl phenyl triazine, N-phenyl melamine, N, N '-phenylbenzene melamine, preferred especially benzoguanamine, promptly 2,4-diamino-6-phenyl-symmetry-triazine, 2,4-diamino-6-benzyloxy-symmetry-triazine.According to prior art, particularly preferred this compound is to contain at least two R that are made up of (not) substituted-amino ₁, R ₂And/or R ₃Group, and/or aromatic group R wherein ₁, R ₂And/or R ₃Form by at least one phenyl ring.Benzoguanamine is particularly preferred.

(bb) specific nitrogenous polymerizable compound: polymine, polyvinylamine, polyallylamine, poly-amino methyl vinylbenzene, poly-amino-ethyl vinylbenzene, by the polyimide resin (for example guanamine resin, melamine resin, guanidine resin, benzoguanamine-melamine resin, aromatic polyamine-melamine resin, urea-melamine resin, urea-benzoguanamine resin) that forms with formaldehyde reaction, the compound that contains hydrazides, poly-amino sulfo-ether, polyureas, poly--5-methylene radical glycolylurea, polypyrrole.

(cc) contain at least one, for example 1-4 triazine ring, preferred 1-2 triazine ring and the particularly spiro-compounds of 2 triazine rings.Preferred especially wherein two compounds that triazine ring has connected by spiro-compounds each other.Triazine ring comprises 1,2,3-triazine, 1,2,4-triazine and 1,3,5-triazines, preferred 1,3,5-triazines.Triazine ring also can comprise substituting group, for example alkyl, for example C ₁-C ₄Alkyl, aryl, amino, or the amino that replaces.As triazine ring, preferably have the triazine ring of amino or substituted-amino, and guanamines ring particularly.The spiral shell structure division can only be made up of carbon atom.The spiral shell structure division that preferably contains one or more heteroatomss, particularly oxygen.The example of these compounds is:

In following formula, alkylidene group R ₁And R ₂The C that comprises branching not or branching ₁-C ₁₀Alkylidene group, for example methylene radical, ethylidene, propylidene, isopropylidene, butylidene and isobutylidene.Arylidene R ₁And R ₂Comprise C ₆-C ₁₀Arylidene, for example phenylene or naphthylidene.Inferior aralkyl R ₁And R ₂Comprise alkylidene group wherein with the group of arylidene keyed jointing.Preferred R ₁And R ₂Group is alkylidene group (C for example ₁-C ₆Alkylidene group), C particularly ₁-C ₃Alkylidene group, for example ethylidene etc.In addition, R ₁And R ₂Can have other substituting group, for example C ₁-C ₆The amino that alkyl (for example methyl), phenyl, amino or N-replace.The object lesson of these spiro-compounds is 3,9-two [(3,5-diamino-2,4,6-triazinyl)-C ₁-C ₆Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane, for example 3, and 9-two [2-(3,5-diamino-2,4, the 6-triazinyl)-and ethyl]-2,4,8,10-four oxaspiros [5.5] undecane (CTU guanamines), 3,9-two [1-(3,5-diamino-2,4,6-triazinyl)-methyl]-2,4,8,10-four oxaspiros [5.5] undecane (CMTU guanamines), 3, [2-(3 for 9-two, 5-diamino-2,4, the 6-triazinyl)-the 2-methylethyl]-2,4,8,10-four oxaspiros [5.51 undecanes, 3, and 9-two [1-(3,5-diamino-2,4, the 6-triazinyl)-1,1-dimethyl methyl]-2,4,8,10-four oxaspiros [5.5] undecane, 3,9-two 13-(3,5-diamino-2,4, the 6-triazinyl)-1, the 1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane and 3, and 9-two [3-(3,5-diamino-2,4, the 6-triazinyl)-2, the 2-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane.In spiro-compounds, preferred 3,9-two [(3,5-diamino-2,4,6-triazinyl)-straight or branched C ₁-C ₅Alkyl]-2,4,8,10-four oxaspiros [5.5] undecane, for example CTU guanamines, CMTU guanamines, 3,9-two [3-(3,5-diamino-2,4,6-triazinyl)-1,1-dimethyl propyl]-2,4,8,10-four oxaspiros [5.5] undecane.Preferred especially CTU guanamines.

(dd) amino acid, for example α-, β-, γ-or δ-amino acid.The example of a-amino acid is the mono amino monocarboxylic acid, for example glycine, L-Ala, valine, positive valine, leucine, nor-leucine, Isoleucine, phenylalanine, tyrosine, diiodotyrosine, N-methyltyrosine, Threonine, Serine, proline(Pro), oxyproline, tryptophane, methionine(Met), Gelucystine, halfcystine, citrulline, butyrine, piperolinic acid, theanine; Mono amino dicarboxylic acid, for example aspartic acid, L-glutamic acid, l-asparagine, glutamine, six hydrogen, two pyridine carboxylic acids, six hydrogen quinolinic acids; Diamino monocarboxylate, for example Methionin, oxylysine, arginine, Histidine.β-, γ-or δ-amino acid whose example be Beta-alanine, beta-aminobutyric acid, six hydrogen quino-melonic acids (hexahydroquinomeronic acid), γ-An Jidingsuan, δ-amino-positive valeric acid.Amino acid can exist with D-, L-or DL-form.Amino acid also can comprise the derivative that carboxyl wherein exists with metallic salt form, and for example the form with an alkali metal salt or alkaline earth salt exists, or exists with the form of acid amides, hydrazides or ester (for example methyl ester or ethyl ester).Amino acid also can load on the porous material, for example loads on silica gel, aluminum oxide, titanium oxide, zirconium white, sepiolite, terre verte, polynite effective constituent, imogolite, zeolite or the activated carbon.Amino acid also can form inclusion complex or have host's inclusion compound, for example have α-, β-, γ-or δ-cyclodextrin.

(ee) has the compound of one or two hydrazides group, the compound that particularly has two hydrazides groups, polymeric dihydrazide compound for example, for example polyacrylic acid hydrazides, or oxalic acid two hydrazides, propanedioic acid two hydrazides, adipic dihydrazide, succinic acid hydrazide ii, pentanedioic acid two hydrazides, pimelic acid two hydrazides, suberic acid two hydrazides, nonane diacid two hydrazides, sebacic dihydrazide, terephthaldehyde's acid dihydrazide, isophthalic dihydrazide.

(ff) poly--Beta-alanine, contain following structural unit:

So, the present invention also provides a kind of moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1) and contain at least a zeolitic material based on the 0.001-10 weight % of component (A1) weight meter in the described moulding compound, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and particle diameter is determined in the 3-7 micrometer range according to ISO 13320, wherein said moulding compound does not contain (aa) compound, (bb) compound, (cc) compound, (dd) compound, (ee) compound and (ff) compound, further preferably the burst size of methanal of described moulding compound is at most 8ppm, preferably be at most 7ppm, more preferably be at most 6ppm, especially preferably be at most 5ppm, for example be 2,3,4 or 5ppm, or for example be 6,7 or 8ppm, measure according to VDA275 in each case.About the further preferred version of zeolitic material, can be referring to foregoing, for example based on the content of the zeolite of polyoxymethylene weight meter, and/or the size of primary crystal, and/or Si: the Al mol ratio, and/or zeolitic material is with the content of H form, and the various combinations of these parameters.

A particularly preferred embodiment of the present invention also provides a kind of moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1) and contain at least a zeolitic material based on the 0.001-10 weight % of component (A1) weight meter in the described moulding compound, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and particle diameter is determined in the 3-7 micrometer range according to ISO 13320, wherein said moulding compound does not contain (cc) compound, further preferably the burst size of methanal of described moulding compound is at most 8ppm, preferably be at most 7ppm, more preferably be at most 6ppm, especially preferably be at most 5ppm, for example be 2,3,4 or 5ppm, or for example be 6,7 or 8ppm, measure according to VDA275 in each case.About the further preferred version of zeolitic material, can be referring to foregoing, for example based on the content of the zeolite of polyoxymethylene weight meter, and/or the size of primary crystal, and/or Si: the Al mol ratio, and/or zeolitic material is with the content of H form, and the various combinations of these parameters.

So the present invention also provides a kind of above-mentioned moulding compound, wherein said moulding compound does not comprise the spiro-compounds with at least one triazine ring.

So the present invention also provides a kind of above-mentioned moulding compound, wherein said moulding compound does not comprise to have and single disperse molar mass distribution and contain at least one primary amino and/or at least one secondary amino group, the preferred organic compound of at least one primary amino.

The present invention also provides a kind of above-mentioned moulding compound, and wherein except at least a polymeric amide, described moulding compound does not comprise to have and singly disperses molar mass distribution and contain at least one amino organic compound.

As mentioned above, for the purposes of the present invention, be surprised to find the described zeolite of used as stabilizers of using in the prior art and can be used as formaldehyde scavenger.So, in moulding compound of the present invention, can not add other formaldehyde scavenger.

So another aspect of the present invention provides the purposes of zeolitic material as the component in the moulding compound that contains at least a polyoxymethylene, be used to reduce the burst size of methanal of moulding compound.So it is a kind of by using at least a zeolitic material to reduce the method for the burst size of methanal of the moulding compound that contains at least a polyoxymethylene as the component of moulding compound that the present invention also provides.

In principle, described purposes can be the polyoxymethylene of any content in moulding compound and the zeolite of any content.For purposes of the present invention, for the character of zeolite and specification also generally without limits, as long as at least a portion zeolite can adsorb bound formaldehyde.

The example that is used for the suitable zeolite of purposes of the present invention is following the composition a) and b) zeolite:

a)Q _X+YAl _XM _YSiO ₄·zH ₂O

Q=Na wherein ⁺, K ⁺, Li ⁺, Cs ⁺, NH4 ⁺, or the mixture formed by two or more these ions;

M=Fe ³⁺, B ³⁺, Ga ³⁺, Ti ⁴⁺, V ⁴⁺, Zn ²⁺Or Ge ⁴⁺, or the mixture of forming by two or more these ions;

X=0-1.0 and

Y＝0-0.05，

Or

b)Q _XAl _XM _YPO ₄·zH ₂O

Q=Na wherein ⁺, K ⁺, Li ⁺, Cs ⁺Or NH ₄ ⁺, or the mixture of forming by two or more these ions;

M=Fe ³⁺, B ³⁺, Li ⁺, Be ²⁺, Mg ²⁺, Ti ⁴⁺, V ⁴⁺, Zn ²⁺, Mn ²⁺, Co ²⁺Or Si ⁴⁺, or the mixture of forming by two or more these ions;

X=0.9-1.0 and

Y＝0-0.10。

Two kinds of structures a) and b) in, z is the molecule number of crystal water, wherein z can be 0 and wherein X and Y can not be 0 simultaneously.Here, the selection of X and Y for example obtains the electronics valence state that equates.

For purposes of the present invention, the example of zeolitic material is A type zeolite, X type zeolite, y-type zeolite, T type zeolite, sodalite, mordenite, analzite, clinoptilolite, chabazite and/or erionite, and wherein these are suitable for absorbing formaldehyde.The example of the zeolite of structure type is the zeolite that is classified as following type by X-ray diffraction: ABW, ACO, AEI, AEL, AEN, AET, AFG, AFI, AFN, AFO, AFR, AFS, AFT, AFX, AFY, AHT, ANA, APC, APD, AST, ASV, ATN, ATO, ATS, ATT, ATV, AWO, AWW, BCT, BEA, BEC, BIK, BOG, BPH, BRE, CAN, CAS, CDO, CFI, CGF, CGS, CHA, CHI, CLO, CON, CZP, DAC, DDR, DFO, DFT, DOH, DON, EAB, EDI, EMT, EPI, ERI, ESV, ETR, EUO, FAU, FER, FRA, GIS, GIU, GME, GON, GOO, HEU, IFR, ISV, ITE, ITH, ITW, IWR, IWW, JBW, KFI, LAU, LEV, LIO, LOS, LOV, LTA, LTL, LTN, MAR, MAZ, MEI, MEL, MEP, MER, MFI, MFS, MON, MOR, MSO, MTF, MTN, MTT, MTW, MWW, NAB, NAT, NES, NON, NPO, OBW, OFF, OSI, OSO, PAR, PAU, PHI, PON, RHO, RON, RRO, RSN, RTE, RTH, RUT, RWR, RWY, SAO, SAS, SAT, SAV, SBE, SBS, SBT, SFE, SFF, SFG, SFH, SFN, SFO, SGT, SOD, SSY, STF, STI, STT, TER, THO, TON, TSC, UEI, UFI, UOZ, USI, UTL, VET, VFI, VNI, VSV, WEI, WEN, YNU, YUG or ZON, as mentioned above.

In these structures, the structure that classifies as BEA, FER, FAU, LTA, MEL, MFI or MOR type by X-ray diffraction is particularly preferred for purposes of the present invention.Also can mention the mixed structure of being made up of two or more these types, example is to have the zeolitic material that mixes the MEL/MFI mixed structure.The zeolitic material of preferred especially LTA type.

Preferred zeolitic material is that bore dia is 0.3-0.5nm, preferred 0.31-0.49nm, more preferably 0.32-0.48nm, more preferably 0.33-0.47nm, more preferably those of 0.34-0.46nm, preferred especially 0.35-0.45nm for purposes of the present invention.For example, particularly preferred bore dia is 0.36nm, or 0.37nm, or 0.38nm, or 0.39nm, or 0.40nm, or 0.41nm, or 0.42nm, or 0.43nm, or 0.44nm, measures according to DIN66134 and DIN66135 in each case.

So in the present invention and in such use, the bore dia of zeolitic material is measured according to DIN66134 and DIN66135 in the 0.3-0.5nm scope.So, the present invention also provides by using at least a zeolitic material to reduce the aforesaid method of the burst size of methanal of the moulding compound that contains at least a polyoxymethylene as the component of moulding compound, wherein the bore dia of zeolitic material is measured according to DIN66134 and DIN66135 in the 0.3-0.5nm scope.

Preferred other zeolitic material is to be 3.0-7.0 micron, preferred 3.1-6.9 micron, more preferably 3.2-6.8 micron, more preferably 3.3-6.7 micron, more preferably 3.4-6.6 micron, more preferably 3.5-6.5 micron, more preferably 3.6-6.4 micron, more preferably 3.7-6.3 micron, more preferably 3.8-6.2 micron, more preferably those of 3.9-6.1 micron, preferred especially 4.0-6.0 micron according to the particle diameter that ISO 13320 measures for purposes of the present invention.

So in the present invention and in such use, the particle diameter of zeolitic material is measured according to ISO 13320 in the 3-7 micrometer range.So, it is a kind of by using at least a zeolitic material to reduce the aforesaid method of the burst size of methanal of the moulding compound that contains at least a polyoxymethylene as the component of moulding compound that the present invention also provides, wherein the particle diameter of zeolitic material is measured according to ISO 13320 in the 3-7 micrometer range.

Purpose for purposes of the present invention, the formaldehyde releasing value that contains the moulding compound of polyoxymethylene preferably is at most 8ppm, more preferably be at most 7ppm, more preferably be at most 6ppm, more preferably be at most 5ppm, for example be 2ppm, 3ppm, 4ppm or 5ppm, or for example 6ppm, 7ppm or 8ppm, measure by VDA275 in each case.

So in the present invention with in such use, the formaldehyde releasing value of moulding compound is eased down to is at most 8ppm, preferably is at most 7ppm, measures according to VDA275.So, it is a kind of by using at least a zeolitic material to reduce the aforesaid method of the burst size of methanal of the moulding compound that contains at least a polyoxymethylene as the component of moulding compound that the present invention also provides, wherein the formaldehyde releasing value of moulding compound is eased down to and is at most 8ppm, preferably be at most 7ppm, measure according to VDA275.

For purposes of the present invention, particularly preferably be, the moulding compound that contains polyoxymethylene does not contain (aa) compound, (bb) compound, (cc) compound, (dd) compound, (ee) compound and (ff) compound, do not comprise (cc) compound especially, more preferably do not comprise spiro-compounds with at least one triazine ring, and/or do not comprise to have and single disperse molar mass distribution and contain at least one primary amino and/or at least one secondary amino group, the organic compound of preferred at least one primary amino, and/or except that at least a polymeric amide, do not comprise and have single dispersion molar mass distribution and contain at least one amino compound.

For purposes of the present invention further preferably, the amount that contains the moulding compound mesolite material of polyoxymethylene is 0.002-9 weight %, more preferably 0.003-8 weight %, more preferably 0.004-7 weight %, more preferably 0.005-6 weight %, more preferably 0.006-5 weight %, more preferably 0.007-4 weight %, more preferably 0.008-3 weight %, more preferably 0.009-2 weight %, more preferably 0.01-1 weight %, more preferably 0.02-0.9 weight %, more preferably 0.03-0.8 weight %, more preferably 0.04-0.7 weight %, more preferably 0.05-0.6 weight % and especially preferably 0.05-0.50 weight % are in each case based on the polyoxymethylene total amount meter that exists in the moulding compound.Here, the amount of the polyoxymethylene that exists as component (A1) in moulding compound is preferred 10-99.999 weight %, more preferably 15-99.999 weight %, more preferably 20-99.99 weight %, more preferably 25-99.9 weight %, more preferably 30-99 weight %, the more preferably component (A1) of 35-98.5 weight %, preferred especially 40-98 weight %, in each case based on the gross weight meter of moulding compound.Moulding compound also can contain 15-99.999 weight %, more preferably 20-99.99 weight %, more preferably 25-99.9 weight %, more preferably 30-99.7 weight %, more preferably the polyoxymethylene of 35-99.6 weight %, preferred especially 40-99.5 weight % is as component (A1), in each case based on the gross weight meter of moulding compound.

Except above-mentioned zeolitic material and at least a polyoxymethylene, moulding compound of the present invention also can contain maximum 89.99 weight %, preferred 0.5-89.99 weight %, more preferably 1-89.99 weight %, more preferably 1-80 weight %, more preferably 1-70 weight %, more preferably 1-60 weight %, more preferably other component of 1-50 weight % and preferred especially 1-40 weight %, based on the gross weight meter of moulding compound.

The example of these additives can be stablizer, filler, dyestuff and other material commonly used in polyoxymethylene moulding compositions.

According to a preferred embodiment of the invention, moulding compound also contains at least a stablizer as component (D1).For the purposes of the present invention, stablizer is the compound that can suppress or reduce the level of the oxidation of at least a polyoxymethylene or photoxidation and/or suppress or reduce the level of the oxidation of at least a other component or photoxidation.

For the purposes of the present invention, the preferred especially stablizer that uses is a sterically hindered phenol for example.Here, suitable sterically hindered phenol is general any compound that has the phenol structure and have at least one bulky group on the phenol ring.

In this compounds, can mention monocycle and polycyclic sterically hindered phenol especially.Under the situation of many ring sterically hindered phenol, corresponding ring is by for example alkyl or the alkyl keyed jointing by sulfur atom-containing.

The example that is preferred for compound of the present invention is those of following formula structure:

R wherein ¹And R ²Be identical or different, R wherein ¹And R ²Be the alkyl of alkyl, replacement or the triazolyl of replacement.R ³Be the amino of alkyl, alkoxyl group or the replacement of alkyl, replacement.The stablizer of described type (antioxidant) for example is described among DE 27 02 661A1 or the US 4,360,617, and the example that can mention is 2,6-di-t-butyl-p-Cresol.

Another kind of preferred sterically hindered phenol is derived from the benzene carboxylic acid, the particularly phenylpropionic acid of Qu Daiing that replace.

Particularly preferred this compounds is a following formula: compound:

R wherein ₄, R ₅, R ₇And R ₈Group can be the alkyl with 1,2,3,4,5,6,7 or 8 carbon atom independently of one another, and it can randomly have substituting group.R ₄, R ₅, R ₇And R ₈In the group at least one is bulky group, the nonactive group of for example preferred sec.-propyl, the tertiary butyl, phenyl or corresponding size.R ₆The aliphatic divalent group that preferably has 1,2,3,4,5,6,7,8,9 or 10 carbon atom also can have the C-O key in main chain.

For the purposes of the present invention, especially preferably have following structure as the compound of component (D1):

R wherein ₄=R ₇=the tertiary butyl, R ₅=R ₈=methyl, and/or

R wherein ₄=R ₅=R ₇=R ₈=the tertiary butyl.

Other example of sterically hindered phenol is: 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 1, [3-(3 for 6-hexylene glycol two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], [3-(3 for tetramethylolmethane base four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], 3,5-di-tert-butyl-hydroxy phenyl phosphonic acids distearyl ester, 3,5-di-t-butyl-4-hydroxyl hydrogen styracin 2,6,7-trioxa-1-phospha dicyclo [2.2.2]-Xin-4-ylmethyl ester, 3,5-di-t-butyl-4-hydroxyl hydrogen styracin 3,5-di-tert-butyl-hydroxy phenyl ester, 3,5-di-t-butyl butyl phenyl-5-chlorobenzotriazole, 2,6-di-t-butyl-4-hydroxymethyl phenol, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 4,4 '-methylene radical two (2,6 di t butyl phenol), 3,5-di-tert-butyl-4-hydroxyl benzyl dimethyl amine and N, N '-hexa-methylene two-3,5-di-t-butyl-4-hydroxyl hydrogen cinnamide.

For the purposes of the present invention, preferred especially 2,2 '-methylene radical two (4-methyl-6-tert butyl phenol), 1, [3-(3 for 6-hexylene glycol two, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], tetramethylolmethane base four [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] and triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyl) phenyl] propionic ester.

According to the present invention, similarly preferably use the sterically hindered phenol that on the ortho position of phenolic hydroxyl group, has a no more than steric group.Particularly, when the look stability of assessment moulding compound of the present invention, when particularly in scattered light, wearing out for a long time, prove that these sterically hindered phenol are favourable components (D1).

Stablizer can use separately or use with the form of mixtures of being made up of two or more different compounds, its preferable amount is 0.005-2 weight %, more preferably 0.01-1.0 weight %, preferred especially 0.05-0.6 weight % is in each case based on the weight meter of component (A1).

So the present invention also provides a kind of above-mentioned moulding compound, wherein moulding compound also contains stablizer based on component (A1) weight meter 0.005-2 weight % as component (D1), preferred sterically hindered phenol, and the more preferably sterically hindered phenol of following formula structure,

Particularly be selected from following sterically hindered phenol: 2,2,-methylene radical two (4-methyl-6-tert butyl phenol), 1, [3-(3 for 6-hexylene glycol two, the 5-di-tert-butyl-hydroxy phenyl) [3-(3 for propionic ester 1, tetramethylolmethane base four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] and triglycol two [3-(the 3-tertiary butyl-5-methyl-4-hydroxyl) phenyl] propionic ester, and by two kinds, three kinds or four kinds of mixtures that these compounds are formed.

In moulding compound, the weight ratio of component (D1) and zeolitic material preferably 20: 1 to 1: 10, more preferably 10: 1 to 1: 5, preferred especially 7: 1 to 1: 2.

So the present invention also provides a kind of above-mentioned moulding compound, wherein component (D1) is a sterically hindered phenol, and the weight ratio of sterically hindered phenol and zeolitic material is 7: 1 to 1: 2.

For example, preferred 4: 1 to 1: 2 scope.

According to another preferred embodiment of the present invention, randomly except component (D1), moulding compound also contains at least a polymeric amide as component (D2).

The example of suitable polymeric amide is hypocrystalline or unbodied resin according to the present invention, for example is described in Encyclopedia of Polymer Science and Engineering, the 11st volume, John Wiley﹠amp; Sons, Inc., 1988, those of 315-489 page or leaf.The fusing point of polymeric amide used according to the invention preferably is lower than 225 ℃, more preferably less than 215 ℃.

The example of suitable polyamides is the polyhexamethylene pelargonamide, the polyhexamethylene decyl amide, polyhexamethylene dodecane diamide, the amino undecanoic amide of poly--11-, with two (right-aminocyclohexyl) methane dodecane diamide, or the product that obtains via the ring-opening reaction of lactan, for example polylauryllactam.Other suitable polymeric amide be based on terephthalic acid or m-phthalic acid as acid constituents and/or trimethylhexamethylenediamine or two (to aminocyclohexyl) propane as those of diamine components, and via the polymeric amide parent resin of the copolymerization of two or more above-mentioned polymkeric substance or its component.

The specially suitable polymeric amide that can mention is based on hexanolactam, hexamethylene-diamine, p, the copolyamide of p '-diamino-dicyclohexyl methane and hexanodioic acid.These example is with trade(brand)name Ultramid_1C, Ultramid_C31, Ultramid_C31 01 and Ultramid_C33 product sold (from BASF Aktiengesellschaft).

Other suitable polymeric amide is with trade(brand)name Elvamide_ product sold (from DuPont).

The preparation of these polymeric amide also is described in the above-mentioned publication.Mole that can be by changing Initiation house thing is the amino ratio with the end acidic group of control end recently.

Polymeric amide can use separately or use with the form of mixtures of being made up of two or more different compounds, its preferable amount is 0.001-2 weight %, more preferably 0.005-1.2 weight %, preferred especially 0.01-0.08 weight % is in each case based on the weight meter of component (A1).

So the present invention also provides a kind of above-mentioned moulding compound, wherein randomly except component (D1), described moulding compound also contains at least a polymeric amide based on component (A1) weight meter 0.001-2 weight % as component (D2).

In moulding compound, the weight ratio of zeolitic material and component (D2) preferably 1: 1 to 1: 25, more preferably 1: 1 to 1: 15, preferred especially 1: 1 to 1: 5.

In some cases, the dispersiveness of used polymeric amide can be by using by 2 jointly, and the polycondensate that 2-two (4-hydroxy phenyl) propane (dihydroxyphenyl propane) and Epicholorohydrin are formed improves.

These polycondensates of being made up of Epicholorohydrin and dihydroxyphenyl propane can obtain from commerce.The trade(brand)name of polycondensate is Phenoxy_ (Union Carbide Corporation) or Epikote_ (Shell).The molecular weight of polycondensate can change in wide region, and any in principle can be suitable from the type of commercial acquisition.

According to another preferred embodiment of the present invention, randomly except component (D1) and/or (D2), moulding compound also contains at least a alkaline earth metal silicate and/or a kind of alkaline-earth metal glycerophosphate as component (D3).

Moulding compound of the present invention preferably contains 0.002-2.0 weight %, more preferably at least a alkaline earth metal silicate and/or a kind of alkaline-earth metal glycerophosphate of 0.005-0.5 weight %, preferred especially 0.01-0.3 weight %, in each case based on the weight meter of component (A1).

For the purposes of the present invention, especially preferably use Calucium Silicate powder, neurosin, Magnesium Silicate q-agent and magnesium glycerophosphate.Magnesium Silicate q-agent and magnesium glycerophosphate are particularly preferred.

The common alkaline earth metal silicate that preferably has following structure:

MeO·xSiO ₂·nH ₂O

Wherein

Me is an alkaline-earth metal, preferred calcium and magnesium, particularly magnesium,

X is the number of 1.4-10, preferred 1.4-6 and

N is the number more than or equal to 0, preferred 0,1,2,3,4,5,6,7 or 8.

Particularly preferred silicate and glycerophosphate can followingly characterize:

Calucium Silicate powder and Magnesium Silicate q-agent each naturally:

The content of CaO and MgO is respectively: 4-32 weight %, and preferred 8-30 weight %, particularly 12-25 weight %,

SiO ₂Ratio and SiO to CaO ₂Ratio (mol/mol) to MgO is respectively: 1.4-10, and preferred 1.4-6, particularly 1.4-4,

Volume density: 10-80g/100ml, preferred 10-40g/100ml and median size are less than 100 microns, preferably less than 50 microns.

Neurosin and magnesium glycerophosphate each naturally:

The content of CaO and MgO is respectively: greater than 70 weight %, be preferably greater than 80 weight %, light residual volume: 45-65 weight %,

Fusing point: be higher than 300 ℃ and

Median size is less than 100 microns, preferably less than 50 microns.

So, the present invention also provides a kind of above-mentioned moulding compound, randomly except component (D1) and/or (D2), described moulding compound also contains based at least a alkaline earth metal silicate of component (A1) weight meter 0.002-2 weight % and/or a kind of alkaline-earth metal glycerophosphate as component (D3).

Described weight percent is based on the gross weight of used all alkaline earth metal silicates and alkaline-earth metal glycerophosphate.

According to another preferred embodiment of the present invention, randomly except component (D1) and/or component (D2) and/or component (D3), moulding compound also contains following material as component (D4):

-at least a saturated or unsaturated aliphatic carboxylic acid and at least a polyvalent alcohol or the ester that obtains with at least a radical of saturated aliphatic alcohol reaction that can be by at least a 10-40 of a having carbon atom with 2-40 carbon atom,

The acid amides of-at least a saturated or unsaturated aliphatic carboxylic acid and amine reaction acquisition that can be by at least a 10-40 of a having carbon atom with 2-20 carbon atom,

-at least a the ether that can pass through at least a alcohol and the acquisition of at least a reacting ethylene oxide.

Preferred use can by at least a 12-30 of having, more preferably 14-24, particularly 16-22 carbon atom saturated or unsaturated aliphatic carboxylic acid and at least a polyvalent alcohol or with at least a have 2-30, more preferably 2-20, more preferably 2-10, particularly the radical of saturated aliphatic alcohol of 2-6 (for example 2,3,4,5 or 6) carbon atom reacts the ester of acquisition.

Preferred use can by at least a 12-30 of having, more preferably 14-24, particularly 16-22 carbon atom saturated or unsaturated aliphatic carboxylic acid with have 2-10, the acid amides of the amine reaction acquisition of 2-6 (for example 2,3,4,5 or 6) carbon atom particularly.

The carboxylic acid that is used to prepare ester and/or acid amides can be monocarboxylic acid or dicarboxylic acid.The example that can mention is n-nonanoic acid, palmitinic acid, lauric acid, margaric acid, dodecanedioic acid, docosoic acid and preferred especially stearic acid, capric acid and montanic acid (mixture with lipid acid of 30-40 carbon atom).

Fatty alcohol can be that monobasic is to quaternary.The example of alcohol is propyl carbinol, n-Octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol and tetramethylolmethane, preferably glycerine and tetramethylolmethane.

Aliphatic amine can be that monobasic is to ternary.The example of amine is stearylamine, quadrol, propylene diamine, hexamethylene-diamine and two (the amino hexyl of 6-) amine, preferred especially quadrol and hexamethylene-diamine.

Correspondingly, preferred ester and acid amides are Stearic diglyceride, tristearin, quadrol SUNSOFT Q-182S, glycerine monopalmitate, trilaurin, glycerine list mountain Yu's acid esters and pentaerythritol tetrastearate.

Also can use the mixture of different esters or acid amides or the mixture of ester and combination acid amides, according to any required mixture ratio.

Other suitable compound is Aethoxy Sklerol and polyesterols, and it is by monocarboxylic acid or poly carboxylic acid, preferred fatty acid esterification, perhaps by etherificate.Suitable product can obtain from commerce, for example from the Loxiol_EP728 of Henkel KGaA.

The preferred ether of derive from alcohol and oxyethane has following general formula:

RO-(CH ₂-CH ₂-O) _n-H

Wherein R is the alkyl with 6-40 carbon atom, and n is the integer more than or equal to 1.

The special preferably saturated C of R ₁₆-C ₁₈Fatty Alcohol(C12-C14 and C12-C18), wherein n is 50, this alcohol can obtain as Lutensol_AT50 from BASF.

The amount of component in moulding compound of the present invention (D4) is 0.01-5 weight % preferably, more preferably 0.09-2 weight %, and preferred especially 0.1-0.7 weight % is based on the weight meter of component (A1).

Described here weight % is based on the gross weight as ester, acid amides and the ether of component (D4).

So, the present invention also provides a kind of above-mentioned moulding compound, wherein randomly except component (D1) and/or component (D2) and/or component (D3), moulding compound also contains based on the following material of component (A1) weight meter 0.01-5 weight % as component (D4):

-at least a saturated or unsaturated aliphatic carboxylic acid and at least a polyvalent alcohol or the ester that obtains with at least a radical of saturated aliphatic alcohol reaction that can be by at least a 10-40 of a having carbon atom with 2-40 carbon atom,

The acid amides of-at least a saturated or unsaturated aliphatic carboxylic acid and amine reaction acquisition that can be by at least a 10-40 of a having carbon atom with 2-20 carbon atom,

-at least a the ether that can pass through at least a alcohol and the acquisition of at least a reacting ethylene oxide.

According to another preferred embodiment of the present invention, randomly except component (D1) and/or component (D2) and/or component (D3) and/or component (D4), moulding compound also contains talcum as component (C).

Talcum is a hydrated magnesium silicate, and its composition is Mg ₃[(OH) ₂/ Si ₄O ₁₀] or MgO4SiO ₂H ₂O.This three layers of phyllosilicate have three tiltedly, monocline or quadrature crystallized form, have the stratiform feature.Also can there be Mn, Ti, Er, Ni, Na and/or K, preferably as trace elements.The OH group also can be substituted into to a certain degree by fluorochemical.Especially preferably using particle diameter is 100%＜20 micron talcum.Size distribution detects via analysis by sedimentation (DIN 6616-1) usually, preferably:

＜20 micron 100 weight %

＜10 micron 99 weight %

＜5 micron 85 weight %

＜3 micron 60 weight %

＜2 micron 43 weight %

This product can obtain (Norwegian TalcMinerals) with Micro-Talc I.T. commercial.

Moulding compound of the present invention preferably contains 0.01-5 weight %, more preferably 0.01-4 weight %, the more preferably talcum of 0.01-3 weight %, preferred especially 0.02-2 weight %, based on the weight meter of component (A1).

So, the present invention also provides a kind of above-mentioned moulding compound, wherein randomly except component (D1) and/or component (D2) and/or component (D3) and/or component (D4), moulding compound also contains talcum based on component (A1) weight meter 0.01-5 weight % as component (c).

According to another preferred embodiment of the present invention, with described zeolite, moulding compound of the present invention contains at least a other nucleator as other component (D5).Moulding compound of the present invention preferably contains 0.0001-1 weight %, more preferably other nucleator of 0.001-0.8 weight %, preferred especially 0.01-0.3 weight %, based on the weight meter of component (A1).Operable nucleator is any known compound that is used for this purpose, for example is melamine cyanurate, boron compound, boron nitride for example, silica, pigment, for example Heliogen Blue_ (CuPc pigment; The registered trademark of BASF Aktiengesellschaft).

So, the present invention also provides a kind of above-mentioned moulding compound, wherein randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (C), moulding compound also contains at least a other nucleator based on component (A1) weight meter 0.0001-1 weight % as component (D5).

Term " nucleator " expression that is used for the present invention can improve the nucleated compound of the crystallization rate of semi-crystalline polymer (for example polyoxymethylene).In this respect, can be with reference to H.Zweifel (editor), " Plastic Additives Handbook " the 5th edition, Hanser Verlag, Munich﹠amp; Cincinnati, 2001, the 18 chapters " Nucleating Agents for SemicrystallinePolymers ", the 949th page is risen, particularly the 956-969 page or leaf.Kunststoffhandbuch 3/1, " Polycarbonate, Polyacetals, Polyester, Celluloseester " [polycarbonate, polyacetal, polyester, cellulose ester], Hanser Verlag, Munich﹠amp; Vienna, 1992,323 pages of concrete data that also provided about polyoxymethylene of the mat woven of fine bamboo strips.

According to another preferred embodiment of the present invention, moulding compound of the present invention contains at least a appropriate filler as other component (D6).Moulding compound of the present invention preferably contains the filler of maximum 50 weight %, preferred 5-40 weight %, based on the weight meter of component (A1).The suitable filler that can mention for example is potassium titanate palpus crystalline substance, wollastonite, carbon fiber, preferred glass fibers, wherein glass fibre is the form of glass fabric, glass isolator, glass non-woven fabric and/or glass yarn rove for example, be that the weak point that 5-200 micron, the low alkalinity E glass of preferred 8-50 micron are formed is cut glass yarn perhaps by diameter, the mean length of bat wool preferably 0.05-1mm, particularly 0.1-0.5 micron after introducing.

The example of other appropriate filler is lime carbonate or granulated glass sphere, preferably the form of Yan Moing, the perhaps mixture of these fillers.

So, the present invention also provides a kind of above-mentioned moulding compound, wherein randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (C), moulding compound also contains at least a filler based on maximum 50 weight % of component (A1) weight meter as component (D6).

According to another preferred embodiment of the present invention, randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (D6), moulding compound of the present invention also contains at least a thermoplastic polyurethane (TPU) as other component of the present invention (A2).This at least a thermoplastic polyurethane is more preferably as impact modified polymkeric substance.

Moulding compound of the present invention preferably contains maximum 55 weight %, more preferably maximum 50 weight %, the particularly component of maximum 45 weight % (A2), in each case based on the weight meter of component (A1).Moulding compound of the present invention preferably contains at least 10 weight %, the more preferably component of at least 12 weight % (A2), in each case based on the weight meter of component (A1).Moulding compound of the present invention preferably contains 10-55 weight %, the more preferably component of 12-45 weight % (A2), in each case based on the weight meter of component (A1).

Thermoplastic polyurethane used in moulding compound of the present invention preferably obtains by following method.

For example, TPU can be by (a) isocyanic ester and (b) is that reaction between the compound of 500-10000g/mol obtains to responding property of isocyanic ester and molar mass, if with suitable and (c) molar mass be the chainextender reaction of 50-499g/mol, if suitable (d) catalyzer and/or (e) conventional auxiliary agent and/or additive in the presence of carry out.Wherein, component (e) also is a hydrolysis stabilizer, for example polymerization and low-molecular-weight carbon imide.

The feed composition and the method that are used to prepare optimization polyurethane will be described by following example.Commonly used component (a) and (b) and optional (c), (d) and/or (e) will be by following example description in preparation urethane:

A) operable organic isocyanate (a) is known aliphatic series, alicyclic, the isocyanic ester of araliphatic and/or aromatics, for example three-, four-, five, six-, seven-and/or eight-methylene diisocyanate, 2-methyl pentamethylene 1, the 5-vulcabond, 2-ethyl butylidene 1,4-vulcabond, pentamethylene 1, the 5-vulcabond, butylidene 1,4-vulcabond, 1-isocyanate group-3,3,5-trimethylammonium-5-isocyanatomethyl hexanaphthene (isophorone diisocyanate, IPDI), 1,4-and/or 1,3-two (isocyanatomethyl) hexanaphthene (HXDI), hexanaphthene 1,4-vulcabond, 1-methylcyclohexane 2,4-and/or 2,6-vulcabond, and/or dicyclohexyl methyl hydride 4,4 '-, 2,4 '-and 2,2 '-vulcabond, ditan 2,2 '-, 2,4 '-and/or 4,4 '-vulcabond (MDI), naphthylidene 1,4-vulcabond (NDI), toluene 2,4-and/or 2,6-vulcabond (TDI), diphenylmethanediisocyanate, 3,3 '-dimethyl diphenyl vulcabond, 1,2-diphenylethane vulcabond, and/or phenylene vulcabond.

B) operable compound (b) is the known compound to responding property of isocyanic ester, for example polyester polyol, polyether glycol and/or polycarbonate diol, these are categorized in the term " polyol " usually, and molar mass is 500-8000g/mol, preferred 600-6000g/mol, 800-4000g/mol and preferably have 1.8-2.3, preferred 1.9-2.2, particularly 2 average functionality particularly.The preferred polyether glycol that uses, for example based on those of known initial substance and conventional oxirane, conventional oxirane is for example oxyethane, propylene oxide and/or butylene oxide ring, is preferably based on 1, the polyether glycol of 2-propylene oxide and/or butylene oxide ring, particularly polyoxy tetramethylene glycol.The advantage of polyether glycol is that its resistance to hydrolysis is greater than polyester polyol.

C) used chainextender (c) can comprise that known molar mass is aliphatic series, araliphatic, aromatics and/or the alicyclic compound of 50-499g/mol, preferred difunctional compound, diamines and/or in alkylidene group, have the alkanediol of 2-10 carbon atom for example, particularly 1,4-butyleneglycol, 1, the 6-hexylene glycol, and/or have two of 3-8 carbon atom-, three-, four-, five-, six-, seven-, eight-, nine-and/or ten-aklylene glycol, preferably oligomeric accordingly-and/or polymerization propylene glycol, also can use the mixture of chainextender.

D) can promote that especially the NCO group of vulcabond (a) and the suitable catalyst of structural constituent (b) and hydroxyl reaction (c) are tertiary amines commonly used in the prior art, triethylamine for example, dimethylcyclohexylam,ne, N-methylmorpholine, N, N '-lupetazin, 2-(dimethylamino ethoxy)-ethanol, diazabicyclo [2.2.2] octane etc., also organometallic compound particularly, titanium ester for example, iron cpd, acetylacetonate iron for example, tin compound, oxalic acid tin for example, two stannous octoates, two lauric acid tin, or the dialkyltin salts of aliphatic carboxylic acid, for example dibutyltin diacetate, dibutyl tin laurate etc.The common consumption of catalyzer is 0.0001-0.1 weight part/100 weight part polyols (b).

E), also can in structural constituent (a) to (c), add conventional auxiliary agent and/or additive (e) with catalyzer (d).For example, can mention surfactant, filler, fire retardant, nucleator, antioxidant, lubricant and releasing agent, dyestuff and pigment, except that inhibitor of the present invention if other suitable stablizer, for example to hydrolysis, light, heat or the activated stablizer that decolours, inorganic and/or organic filler, toughener, and softening agent.In a preferred embodiment, component (e) also can comprise hydrolysis stabilizer, for example polymerization and low-molecular-weight carbon imide.

With described component a) and b) and optional c), d) and e), also can use chain regulator, have the molecular weight of 31-499g/mol usually.These chain regulators are only to have a compound to the functional group of responding property of isocyanic ester, and example is monofunctional alcohol, monofunctional amines and/or simple function polyvalent alcohol.These chain regulators can be used for controlledly regulating the flowing property of TPU.The consumption of chain regulator is the 0-5 weight part normally, and preferred 0.1-1 weight part is based on the components b of 100 weight parts) meter, and chain regulator is defined as amount of component b) a part.

Other details about above-mentioned auxiliary agent and additive can find in technical literature.

Structural constituent (b) and mol ratio (c) can change in wide region to regulate the hardness of TPU.Proved that successful mol ratio is that component (b) is 10: 1 to 1: 10 with respect to used chainextender (c) total amount, particularly 1: 1 to 1: 4, here, the hardness of TPU increased along with the increase of (c) content.

Chainextender (c) also can be preferred for preparing TPU.

This reaction adopts conventional index to carry out, and preferred index is 60-120, and preferred especially index is 80-110.Index definition for the sum of during reaction used isocyanate groups in component (a) and in component (b) and (c) to the ratio between the group of responding property of isocyanic ester (promptly to reactive hydrogen atom).If index is 100,, in component (b) with (c) reactive hydrogen atom is arranged, i.e. a functionality to responding property of isocyanic ester then for for each isocyanate groups in the component (a).If index is higher than 100, then have than the more isocyanate groups of OH group.

TPU can prepare continuously by known method, for example uses reactive extruder or by the belt method, by once-through method or prepolymer method, or carries out off and on by known prepolymer process.Component (a) and (b) in these methods and optional (c), (d) and/or (e) can mix successively or mix simultaneously each other, this moment, reaction began immediately.

In the forcing machine method, structural constituent (a) and (b) and optional (c), (d) and/or (e) introduced in the forcing machine individually or with form of mixtures, for example react under 100-280 ℃, preferred 140-250 ℃ temperature, the TPU of gained extrudes, cooling and granulation.

For the purposes of the present invention, component utilized (A2) very particularly preferably contains the thermoplastic poly ester polyurethane, and the Durometer A hardness of measuring according to DIN53505 is 75-90.Preferred component is MDI (diphenylmethanediisocyanate) and the polyester be made up of hexanodioic acid and butyleneglycol in these thermoplastic poly ester polyurethanes.

For example, other the suitable elastomerics that can mention is the thermoplastic polyurethane of for example describing in EP 0 115 846A2, EP0115 847A2 and EP 0 117 664A1.

So, the present invention also provides a kind of above-mentioned moulding compound, randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (D6) and/or (C), described moulding compound also contains at least a urethane of maximum 50 weight % as component (A2), based on the weight meter of component (A1).

The present invention also more preferably provides a kind of above-mentioned moulding compound, randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (D6) and/or (C), described moulding compound also contains at least a thermoplastic polyurethane of maximum 50 weight % as component (A2), based on the weight meter of component (A1).

So, the present invention also provides a kind of above-mentioned moulding compound, randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (C), described moulding compound also contains at least a thermoplastic poly ester polyurethane of maximum 50 weight % as component (A2), measure according to DIN53505, the Xiao A hardness of described thermoplastic poly ester polyurethane is 75-90, based on the weight meter of component (A1).

According to another embodiment of the invention, randomly and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (D6) except component (D1), (C) and/or (A2), described moulding compound also contains at least a elastomeric polymer or elastomerics as component (A3).Described at least a elastomeric polymer or elastomerics are more preferably as impact modified polymkeric substance.

In moulding compound of the present invention, the preferably maximum 50 weight % of the amount of component (A3), more preferably maximum 45 weight %, particularly maximum 40 weight % are in each case based on the weight meter of component (A1).

These elastomericss of preferred type are to be known as those of ethylene/propene (EPM) rubber or ethylene/propylene/diene (EPDM) rubber.

EPM rubber is substantially free of residual double bonds usually, and EPDM rubber can have 1-20 two key/100 carbon atoms.

The example of the diene monomers that is used for EPDM rubber that can mention is a conjugated diolefine, for example isoprene and divinyl; Non-conjugated diene with 5-25 carbon atom, for example 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 2,5-dimethyl-1,5-hexadiene and 1,4-octadiene; Cyclic diolefine, for example cyclopentadiene, cyclohexadiene, cyclooctadiene and Dicyclopentadiene (DCPD); And alkenyl norbornylene, for example 5-ethylidene-2-norbornene; With three cyclic diolefines, for example 3-methyl three encircles [5.2.1.0 ^2.6]-3,8-decadiene, and their mixture.Preferred 1,5-hexadiene, 5-ethylidene norbornene and Dicyclopentadiene (DCPD).The diene content of EPDM rubber is 0.5-50 weight % preferably, and more preferably 0.75-20 weight %, particularly 1-8 weight % are based on the gross weight meter of rubber.

EPDM rubber also can be monomer-grafted with other, for example uses (methyl) glycidyl acrylate, (methyl) acrylate and (methyl) acrylamide graft.

Ethene is another kind of preferred rubber with the multipolymer of (methyl) acrylate.These rubber also can contain the monomer of epoxy group(ing).These monomers that contain epoxy group(ing) are preferably by being introduced in the rubber in the monomer adding monomer mixture that contains epoxy group(ing) that will have following general formula I or II:

R wherein ₆To R ₁₀Be hydrogen or alkyl with 1,2,3,4,5 or 6 carbon atom, m is 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20, g is 0,1,2,3,4,5,6,7,8,9 or 10, and p is 0,1,2,3,4 or 5.

R ₆To R ₈Hydrogen preferably, wherein m is 0 or 1, g is 1.Corresponding compounds is glycidyl allyl ether and vinyl glycidyl ether.

Preferred formula (II) compound is the ester of vinylformic acid and/or methacrylic acid, and wherein these esters contain epoxy group(ing), and example is glycidyl acrylate and glycidyl methacrylate.

Multipolymer advantageously is made up of the ethene of 50-98 weight %, the monomer that contains epoxy group(ing) of 0-20 weight %, and its surplus is (methyl) acrylate.

Preferred especially multipolymer composed of the following components:

50-98 weight %, the particularly ethene of 55-95 weight %,

0.1-40 glycidyl acrylate and/or the glycidyl methacrylate of weight %, particularly 0.3-20 weight %, (methyl) acrylic anhydride and/or maleic anhydride and

N-butyl acrylate and/or the 2-ethylhexyl acrylate of 1-50 weight %, particularly 10-40 weight %.

Other preferred (methyl) acrylate be methyl-, ethyl-, propyl group-, isobutyl--and the tertiary butyl-ester.

In addition, operable other monomer is vinyl ester and vinyl ether.

Above-mentioned ethylene copolymer can prepare by known method, is preferably undertaken by the random polymerization under high pressure and high temperature.Suitable method is known.

Other preferred elastomerics is an emulsion polymer, and its preparation example is as being described in D.C.Blackley " Emulsion Polymerization ", Applied Science Publishers LTD, London1975.Operable emulsifying agent and catalyzer are known.

In principle, can use the elastomerics of equal phase structure or have those of shell structure.Shell structure comes to determine by each monomeric interpolation especially in proper order.The morphology of polymkeric substance also is subjected to the influence of this interpolation order.

The monomer that being used for of can mentioning prepares the elastomerics rubber components for example is an acrylate, for example n-butyl acrylate and 2-ethylhexyl acrylate, corresponding methacrylic ester, divinyl and isoprene, and their mixture.These monomers can with other monomer copolymerization, for example vinylbenzene, vinyl cyanide, vinyl ether and with other acrylate or methacrylic ester copolymerization, for example methyl methacrylate, methyl acrylate, ethyl propenoate or propyl acrylate.

Elastomeric soft phase or rubber phase (especially preferably have and be lower than 0 ℃ second-order transition temperature) can be nuclear, skin or middle case (under the elastomerics situation that has more than the structure of two-layer shell).Have elastomerics more than one deck shell and also can have the shell of forming by rubber phase more than one deck.

If in elastomer structure, except that rubber phase, comprise one or more hard components (have and be higher than 20 ℃ second-order transition temperature), then they are usually by vinylbenzene, vinyl cyanide, methacrylonitrile, alpha-methyl styrene, p-methylstyrene or acrylate or methacrylic ester (as methyl acrylate, ethyl propenoate or the methacrylic acid group ester) preparation of polymerization as principal monomer.In addition, can also use other comonomer of less ratio.

Verified, the emulsion polymer that uses the surface to have active group is favourable in some cases.The example of this type group is epoxy group(ing), amino and amide group, and can be by following the functional group that uses the following formula monomer to introduce,

Wherein each substituting group is as giving a definition:

R ¹⁵For hydrogen or have the alkyl of 1,2,3 or 4 carbon atom,

R ¹⁶Be hydrogen, have the alkyl of 1,2,3,4,5,6,7 or 8 carbon atom, or have the aryl of 6,7,8,9,10,11 or 12 carbon atoms, particularly phenyl,

R ¹⁷Be hydrogen, the alkyl with 1,2,3,4,5,6,7,8,9 or 10 carbon atom has the aryl of 6,7,8,9,10,11 or 12 carbon atoms, or-OR ¹⁸,

R ¹⁸For having the alkyl of 1,2,3,4,5,6,7 or 8 carbon atom, or have the aryl of 6,7,8,9,10,11 or 12 carbon atoms, the group that is randomly contained O or N replaces,

X is a chemical bond, has the alkylidene group of 1,2,3,4,5,6,7,8,9 or 10 carbon atom, or has the arylidene of 6,7,8,9,10,11 or 12 carbon atoms, or

Wherein

Y is OZ or NH-Z, and

Z is the alkylidene group with 1,2,3,4,5,6,7,8,9 or 10 carbon atom, or has the arylidene of 6,7,8,9,10,11 or 12 carbon atoms.

The grafted monomer with following structure that EP-A208 187A2 describes also is suitable at surface introducing active group:

Other example that can mention is the acrylate or the methacrylic ester of acrylamide, Methacrylamide and replacement, for example methacrylic acid (N-tertiary butyl amino) ethyl ester, vinylformic acid (N, the N-dimethylamino) ethyl ester, vinylformic acid (N, the N-dimethylamino) methyl esters and vinylformic acid (N, N-diethylin) ethyl ester.

The particle of rubber phase also can be crosslinked.The example of cross-linking monomer is 1, the cyclic monomer compound of describing among 3-divinyl, Vinylstyrene, Phthalic acid, diallyl ester, butylene glycol diacrylate and vinylformic acid dihydro DCPA and EP-A0 050 265A1, it has at least three identical ethylenically unsaturated groups of rate of polymerization, for example be triallyl cyanurate, triallyl isocyanurate, cyanogen urea triethylenetetraminehexaacetic acid alkene ester, triallyl benzene, trivinylbenzene and 1,3,5-three acryloxies six hydrogen-s-triazine.

Can also use to be called as grafting and to connect monomeric monomer, promptly have two or more can be between polymerization period with the monomer of the polymerizable double bonds of different rates reaction.Preferred this compounds that uses: wherein at least one reactive group with the about identical rate aggregation of other monomer, and for example polymerization significantly slowlyer of other reactive group (or a plurality of reactive group).Different rates of polymerization are brought up to certain proportion with the unsaturated double-bond in the rubber.If then with another grafted branches to the rubber of the type, be present in the rubber to two keys of small part and grafted monomer reaction formation chemical bond, promptly had at least to a certain degree and the chemical bonded refractory grafting base mutually by grafted.

Such grafting connects monomeric example for comprising allylic monomer, the allyl ester of ethylene linkage unsaturated carboxylic acid particularly, for example allyl acrylate, allyl methacrylate(AMA), diallyl maleate, diallyl fumarate and methylene-succinic acid diallyl, and the corresponding monoene propylated compound of these dicarboxylic acid.In addition, also exist many other suitable grafting and connect monomer.Further details for example with reference to US-A 4 148 846 (for example the 4th hurdle 56 row are to the 5th hurdle 58 row), are incorporated herein its full content for reference.

The ratio of these cross-linking monomers in impact modified polymkeric substance is generally the highest 5 weight % based on impact modified polymkeric substance meter, preferably is no more than 3 weight %.

Some preferred emulsions polymkeric substance have been listed below.What at first mention here is the graftomer that has core and at least one shell and have following structure:

Core monomer	The coating monomer
		1,3-butadiene, isoprene, n-butyl acrylate, vinylformic acid (ethyl hexyl) ester or their mixture are randomly with grafted monomer	Vinylbenzene, vinyl cyanide, (methyl) methyl acrylate randomly have described reactive group

The graftomer that replacement has the multilayered shell structure, the monoshell elastomerics that can also use uniformly, promptly form by 1,3-butadiene, isoprene and n-butyl acrylate or their multipolymer.These products are also by following the monomer preparation of using cross-linking monomer or having reactive group.

Described elastomerics can also be by other traditional method preparation, for example by suspension polymerization.

Certainly, can also use the mixture of the above-mentioned type rubber.

So, invention also provides a kind of above-mentioned moulding compound, randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (D6) and/or (C) and/or (A2), described moulding compound also contains based at least a elastomeric polymer of maximum 50 weight % of component (A1) weight meter or elastomerics as component (A3).

A preferred embodiment of moulding compound of the present invention comprises component (A2) or component (A3).Another preferred embodiment of moulding compound of the present invention not only comprises component (A2), and comprise component (A3), in this case, a preferred preferred embodiment of moulding compound comprises component (A2) and the component (A3) based on maximum 50 weight % of component (A1) weight meter, and described weight percent is based on (A2) and weight percent summation (A3).

In addition, moulding compound of the present invention can contain conventional additives and processing aid.For example, can mention:

As the softening agent of component (D7), the 0.001-5 weight % that its amount in moulding compound of the present invention is preferably counted based on component (A1);

As the coupling agent of component (D8), the 0.001-5 weight % that its amount in moulding compound of the present invention is preferably counted based on component (A1).As the example of coupling agent, can mention suitable paraffinic hydrocarbons, for example white oil;

As the pigment of component (D9), the 0.001-5 weight % that its amount in moulding compound of the present invention is preferably counted based on component (A1);

At least a 2-hydroxy phenyl benzotriazole derivatives and/or 2 of being selected from as component (D10), 2,6, the compound of 6-tetramethyl--1-piperidine derivative, preferably as the UV stablizer, its amount in moulding compound of the present invention is preferably based on the 0.001-5 weight % of component (A1) meter.Be present in the moulding compound of the present invention and have secondary amine as the compound of fruit component (D10), moulding compound then further preferably of the present invention does not comprise other to have single dispersion molar mass distribution and has the organic compound of secondary amine, and does not comprise the organic compound that has single dispersion molar mass distribution and have primary amine groups.Be present in the moulding compound of the present invention and have secondary amine as the compound of fruit component (D10), moulding compound then further preferably of the present invention does not comprise other and has single organic compound that disperses molar mass distribution and have secondary amine, and do not comprise and have single organic compound that disperses molar mass distribution and have primary amine groups, do not have single organic compound that disperses molar mass distribution and have secondary amine with except optional polymeric amide, not comprising to have single dispersion molar mass distribution and have the organic compound of primary amine groups and do not comprise.

According to a particularly preferred embodiment, the present invention also provides a kind of above-mentioned moulding compound, randomly except component (D1) and/or (D2) and/or (D3) and/or (D4) and/or (D5) and/or (D6) and/or (D7) and/or (D9) and/or (D10) and/or (A2) and/or (A3) and/or (C), described moulding compound also contains the 0.001-5 weight % based on component (A1) weight meter, preferred 0.01-4 weight %, more preferably 0.1-2 weight %, the more preferably at least a coupling agent of 0.2-1 weight %, preferred at least a suitable paraffinic hydrocarbons, more preferably at least a white oil is as component (D8).

Thermoplastic composition of the present invention prepares by mixing each component according to known mode.Zeolitic material can add simultaneously or add afterwards in component (A1).Component (A1) can be before adding zeolitic material, during or pulverize afterwards, grinding or granulation.Before adding zeolitic material, during or afterwards, component (A1) is a liquid form, for example be melt form, the solution form in suitable solvent, or the dispersion form in suitable dispersion medium.

In case (A1) mix with zeolitic material, if there is solvent, removes at least to a certain extent and desolvate, preferably remove fully basically.

As fruit component (C) and (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9) and/or (D10) be not liquid, then they advantageously use with the form of fine grainding.Median size less than 100 microns, preferably be specially suitable less than 50 microns product.Component (C) and (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9) and/or (D10) also can add simultaneously together, perhaps component (A1) afterwards order add, particularly before adding zeolitic material, during or add afterwards.

These components are advantageously mixed in forcing machine, and hybrid technique preferably carries out simultaneously at component (A1) fused.

So, the present invention also provides a kind of method for preparing above-mentioned moulding compound, comprise at least a polyoxymethylene is mixed with zeolitic material, the bore dia of described zeolitic material is determined in the scope of 0.3-0.5nm according to DIN66134 and DIN66135 and the particle diameter of described zeolitic material is determined in the scope of 3-7 micron according to ISO13320.

The present invention also provides a kind of aforesaid method, further comprises the composition that contains polyoxymethylene and zeolitic material is extruded under 100-270 ℃ temperature.

An example of the advantage of extrusion method of the present invention is that used zeolite raw material can comprise the zeolite with high water content, comes it dry via the temperature of selecting in the expressing technique process.This shows does not need zeolitic material is carried out pre-dry pre-treatment.

The present invention also provides a kind of method for preparing above-mentioned moulding compound, may further comprise the steps:

(i), and/or component (A1) is dissolved at least a suitable solvent with component (A1) fusion;

(ii) during (i) and/or afterwards, (A1) mixes with zeolitic material with component;

(iii) randomly, be dissolved at least a solvent, then remove described at least a solvent at least in part according to (i) as fruit component (A1).

The present invention also provides a kind of moulding compound that obtains by aforesaid method.

The term of Shi Yonging " moulding compound " expression in the present invention has the composition of one of above-mentioned composition, and it can be via at least one suitable step deformation.Therefore, moulded product can prepare via the deformation of moulding compound of the present invention.Moulding compound also can be transformed into paper tinsel, film and foams.So moulding compound has favourable mechanical property for this type of purposes.For example, suitably the elastic tensile modulus of enhanced moulding compound (example be via adding glass fibre suitably enhanced moulding compound) is 2400MPa at least, preferred 2600MPa, measure by ISO 527, with their yielding stress be 59.5MPa at least, preferred 62.5MPa at least, preferably 63.0MPa at least measures by ISO 527 in each case.

Moulding compound can carry out molding by forming step, for example by spraying drying, injection moulding, extrude, compression moulding or granulation, obtain moulded product, for example pellet, pearl or sheet stock.

Can produce other moulded product from moulding compound of the present invention.For example, if pellet of the present invention can fusion and at least a suitable additive of suitable interpolation, be processed into other moulded product.The example of appropriate addn be said components (C) and (D1), (D2), (D3), (D4), (D5), (D6), (D7), (D8), (D9) and/or (D10).Also can add at least a zeolitic material in producing other moulded product process, example is above-mentioned preferred zeolite material and/or extra component (A1) and/or (A2) and/or (A3).For example, the preferred component (D6) of further adding, example is a glass fibre, wherein glass fibre can use with the form of glass fabric, glass bunch, glass non-woven fabric and/or glass yarn rove, is that the weak point that 5-200 micron, the low alkalinity E glass of preferred 8-50 micron are formed is cut glass yarn by diameter for example.

So, the present invention also provides a kind of moulded product, it contains at least 10 weight %, preferred at least 20 weight %, the more preferably moulding compound of the present invention of at least 50 weight % and preferred especially at least 90 weight %, for example moulding compound of the present invention of 90,91,92,93,94,95,96,97,98,99 or 100 weight %.

Particularly preferred moulded product is a granulated material according to the present invention, and it contains the moulding compound of the present invention of 100 weight %.Further preferably the particle diameter of granulated material is 1-6mm, more preferably 1.5-5mm, especially preferably 2-4mm.For the shape of moulded product basically without limits, can be cylindrical, lensing, sphere or other Any shape, this depends on concrete production method.

For the purposes of the present invention, especially preferably provide such moulded product, its burst size of methanal is 8ppm at the most, preferred 7ppm at the most, and more preferably 6ppm at the most, particularly 5ppm at the most measure according to VDA275.

Another feature of the such use of moulding compound of the present invention, zeolitic material of the present invention and reduction burst size of methanal is to have utilized another advantageous effect of zeolitic material simultaneously: the nucleogenesis during the preparation moulding compound.

So, the present invention burst size of methanal that zeolitic material, particularly above-mentioned preferred zeolitic material be used to reduce the moulding compound that contains polyoxymethylene also is provided and during the preparation moulding compound simultaneously as the purposes of nucleator.

Another feature of moulding compound of the present invention and moulded product is to have low-down burst size of methanal and while favorable mechanical performance.

Another feature of moulding compound of the present invention and moulded product is to have low-down burst size of methanal and simultaneously good thermal stability.

Another feature of moulding compound of the present invention and moulded product is to have low-down burst size of methanal and simultaneously good thermal stability and favorable mechanical performance.

The example of the feature of preferred moulded product (for example above-mentioned preferred pellet) is in pellet low-down weight loss under the situation that 222 ℃ of temperature wore out 2 hours in nitrogen, this weight loss is at most 0.5%, more preferably at the most 0.4%, for example be 0.1%, 0.2%, 0.3% or 0.4%.

Another example of the feature of preferred moulded product (for example above-mentioned preferred pellet) is in pellet low-down weight loss under the situation that 222 ℃ of temperature wore out 2 hours in air, this weight loss is at most 1.5%, more preferably at the most 1.4%, for example be 1.0%, 1.1%, 1.2%, 1.3% or 1.4%.

In preferred embodiments, moulded product also contains component (A2) and/or the component (A3) of maximum 50 weight %, and/or the component of maximum 40 weight % (D6).

So the present invention also provides a kind of aforesaid method, also comprise described moulding compound processing is obtained moulded product.

So the present invention also provides a kind of moulded product, it obtains by aforesaid method, and its burst size of methanal is 8ppm at the most, and preferably 7ppm at the most measures according to VDA275.

The present invention also provides a kind of above-mentioned moulding compound that is used to prepare moulded product, wherein this moulded product is toy or toy part, or car accessories, aircraft accessory or ship's fitments, or the parts of car accessories, the parts of aircraft accessory or the parts of ship's fitments, or the parts of packing or packing, or the parts of container or container, or the parts of housed device or housed device, or the parts of medical facilities or medical facilities, or the component of toiletry, or the parts of electronics or electric installation, or in building construction used equipment or the parts of this equipment.

The example of concrete purposes is a clip, fastener, spring connector, spring part, loudspeaker element, the valve body of WC system, spray header, roller, lever, sliding surface bearing, pilot bearing (for example sliding top of automobile), gear, actuated element, conditioning equipment, food product pack, cosmetic package and makeup are replaced mechanism's (for example those in lipstick or deodorant), are used for the steaming plant of coffee machine, the conveyor link, groove plug-in unit (flange for example, shockproof cup or groove lid), be used for the framework of fuel filter, sprinkler system, switch is used for the ball cover at juncture, is used for the swing carrier of automobile, the valve that can not return is used for the windshield washer nozzle of automobile, the interior pipe of Bowden cable, the upholder that is used for the automobile sun plate, pressure-button is used for the winding mechanism of securing band, grinding machine, extrapolation chassis, chair back, gas dosing meter (shell of sensing chamber and functional component), insulation composition, filled compositions, window device or door gear, machine element, printer unit, and adornment.

In following preferred embodiment, obtained moulding compound of the present invention, moulded product, method and purposes from following scheme 1-31, comprise the combination of these embodiments:

1. moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1) with based at least a zeolitic material of the weight meter 0.001-10 weight % of the component that exists in the moulding compound (A1), the bore dia of described zeolitic material is determined in the scope of 0.3-0.5nm according to DIN66134 and DIN66135, and the particle diameter of wherein said zeolitic material is determined in the 3-7 micrometer range according to ISO 13320.

2. as enforcement scheme 1 described moulding compound, wherein the bore dia of zeolitic material is in the 0.37-0.43nm scope.

3. as enforcement scheme 1 or 2 described moulding compounds, wherein the particle diameter of zeolitic material is measured according to ISO 13320 in the 4-6 micrometer range.

4. as implementing each described moulding compound among the scheme 1-3, it contains the zeolitic material of 0.05-0.50 weight %, based on the weight meter of the component that exists in moulding compound (A1).

5. as implementing each described moulding compound among the scheme 1-4, wherein according to SiO ₂: Al ₂O ₃Mol ratio calculate the Si of described zeolitic material: the Al mol ratio is in being up to 5: 1 scope.

6. as implementing each described moulding compound among the scheme 1-5, wherein at least 90% of the primary crystal size of zeolitic material is in the scope of 1.5-3.0 micron, measures by SEM.

7. as implementing each described moulding compound among the scheme 1-6, wherein the zeolitic material of at least 75 weight % is not to exist with the H form.

8. as implement each described moulding compound among the scheme 1-7, wherein, according to SiO ₂: Al ₂O ₃Mol ratio is calculated, the Si of zeolitic material: the Al mol ratio is 1: 1 to 2: 1, measure by SEM zeolitic material the primary crystal size at least 95% be in the scope of 1.75-2.75 micron, and the described zeolitic material of at least 95 weight % is not to exist with the H form.

9. as implementing each described moulding compound among the scheme 1-8, wherein said moulding compound does not comprise the spiro-compounds with at least one triazine ring.

10. as implementing each described moulding compound among the scheme 1-9, wherein said moulding compound does not comprise the organic compound that has single dispersion molar mass distribution and contain at least one primary amino and/or at least one secondary amino group.

11. as implement each described moulding compound among the scheme 1-10, wherein said moulding compound also contains stablizer based on component (A1) weight meter 0.005-2 weight % as component (D1).

12. as enforcement scheme 11 described moulding compounds, wherein component (D1) is a sterically hindered phenol, and the weight ratio of sterically hindered phenol and zeolitic material is 7: 1 to 1: 2.

13. as implement each described moulding compound among the scheme 1-12, it also contains at least a polymeric amide based on component (A1) weight meter 0.001-2 weight % as component (D2).

14. as implement each described moulding compound among the scheme 1-13, it also contains based on the alkaline earth metal silicate of component (A1) weight meter 0.002-2 weight % and/or alkaline-earth metal glycerophosphate as component (D3).

15. as implement each described moulding compound among the scheme 1-14, it also contains based on the following material of component (A1) weight meter 0.01-5 weight % as component (D4):

-at least a saturated or unsaturated aliphatic carboxylic acid and at least a polyvalent alcohol or the ester that obtains with at least a radical of saturated aliphatic alcohol reaction that can be by at least a 10-40 of a having carbon atom with 2-40 carbon atom,

The acid amides of-at least a saturated or unsaturated aliphatic carboxylic acid and amine reaction acquisition that can be by at least a 10-40 of a having carbon atom with 2-20 carbon atom,

-at least a the ether that can pass through at least a alcohol and the acquisition of at least a reacting ethylene oxide.

16. as implement each described moulding compound among the scheme 1-15, it also contains talcum based on component (A1) weight meter 0.01-5 weight % as component (C).

17. as implement each described moulding compound among the scheme 1-16, it also contains white oil based on component (A1) weight meter 0.01-5 weight % as component (D8).

18. as each described moulding compound among the scheme of enforcement 1-17, wherein at least a polyoxymethylene is at least a POM-H Acetal homopolymer or at least a polyacetal copolymer, or the mixture of being made up of at least a POM-H Acetal homopolymer and at least a polyacetal copolymer.

19. as implementing each described moulding compound among the scheme 1-18, its at least a urethane that also contains maximum 55 weight % is as component (A2), based on the weight meter of component (A1).

20. as enforcement scheme 19 described moulding compounds, wherein said urethane is the thermoplastic poly ester polyurethane, measures according to DIN53505, the Xiao A hardness of described thermoplastic poly ester polyurethane is 75-90.

21. as implement each described moulding compound among the scheme 1-20, the burst size of methanal of described moulding compound is 8ppm at the most, preferably 7ppm at the most measures according to VDA275.

22. zeolitic material as the purposes of the component in the moulding compound that contains at least a polyoxymethylene, is used to reduce the burst size of methanal of described moulding compound.

23. as enforcement scheme 22 described purposes, the bore dia of wherein said zeolitic material is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135.

24. as enforcement scheme 22 or 23 described purposes, the particle diameter of wherein said zeolitic material is determined in the 3-7 micrometer range according to ISO 13320.

25. as implement each described purposes among the scheme 22-24, be used for the burst size of methanal of described moulding compound is reduced to 8ppm at the most, more preferably 7ppm at the most measures by VDA275.

26. as implement each described purposes among the scheme 22-25, wherein have single disperse molar mass and have primary amine groups and/or the organic compound of secondary amine as the component of the burst size of methanal that is used to reduce described moulding compound in the moulding compound.

27. one kind prepares as implementing the method for each described moulding compound among the scheme 1-21, comprise at least a polyoxymethylene is mixed with zeolitic material, the bore dia of described zeolitic material is according to DIN66134 and DIN66135 is determined in the 0.3-0.5nm scope and the particle diameter of described zeolitic material is determined in the 3-7 micrometer range according to ISO 13320.

28., comprise the composition that contains polyoxymethylene and zeolitic material extruded under 100-270 ℃ temperature as enforcement scheme 27 described methods.

29., also comprise described moulding compound processing is obtained moulded product as enforcement scheme 27 or 28 described methods.

30. a moulded product, its by as the described methods acquisitions of enforcement scheme 29, its burst size of methanal is 8ppm at the most, preferably 7ppm at the most measures according to VDA275.

31. maybe can be used to prepare the purposes of moulded product as each described moulding compound among the enforcement scheme 1-21 by the moulding compound that method as described in embodiment 27 or 28 obtains, wherein said moulded product is toy or toy part, or car accessories, aircraft accessory or ship's fitments, or the parts of car accessories, the parts of aircraft accessory or the parts of ship's fitments, or the parts of packing or packing, or the parts of container or container, or the parts of housed device or housed device, or the parts of medical facilities or medical facilities, or the component of toiletry, or the parts of electronics or electric installation, or in building construction used equipment or the parts of this equipment.

Fig. 1-9 and embodiment are used to illustrate the present invention.

Description of drawings

Fig. 1: the particle diameter ratio that shows zeolitic material of the present invention and contrast material.Shown curve is measured according to ISO 13320.Unit maps in the logarithm mode on X-coordinate for the particle diameter of micron.The transformation % of particle is linear mapping on ordinate zou.

Zeolitic material of the present invention is the LTA type zeolite of na form, according to SiO ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is 1: 1, and has the 8-annular distance, and bore dia is 0.41nm according to DIN66134 and DIN66135 mensuration.This material can obtain that (Purmol 4ST is from Zeochem, CH) from commerce.This material shows with oral thermometer in the drawings.

Contrast material also is the LTA type zeolite of na form, according to SiO ₂: Al ₂O ₃The Si that mol ratio is calculated: the Al mol ratio is 1: 1, and has the 8-annular distance, and bore dia is about 0.4nm according to DIN66134 and DIN66135 mensuration.This material can obtain (Zeosorb 42, from Tricat ZeolitesGmbH, Bitterfeld, Germany) from commerce.This material is represented with Δ in the drawings.

Fig. 2: the micro-photograph of the SE according to 2000: 1 ratio of enlargement that shows material of the present invention (Purmol 4ST is referring to the description of Fig. 1).

Fig. 3: the micro-photograph of the SE according to 10000: 1 ratio of enlargement that shows material of the present invention (Purmol 4ST is referring to the description of Fig. 1).

Fig. 4: the micro-photograph of the SE according to 10000: 1 ratio of enlargement that shows material of the present invention (Purmol 4ST is referring to the description of Fig. 1).

Fig. 5: the micro-photograph of the SE according to 2000: 1 ratio of enlargement that shows contrast material (Zeosorb 42, referring to the description of Fig. 1).

Fig. 6: the micro-photograph of the SE according to 10000: 1 ratio of enlargement that shows contrast material (Zeosorb 42, referring to the description of Fig. 1).

Fig. 7: the micro-photograph of the SE according to 10000: 1 ratio of enlargement that shows contrast material (Zeosorb 42, referring to the description of Fig. 1).

Fig. 8: show the many board molds that are used for measuring burst size of methanal and production sheet material in the present invention according to VD275.The right side of Fig. 8 shows the lateral cross section of many board molds.Above it and below be two spaces, connect via the inlet that extends from right to left each other, and be shaped to frustum-like shape, two feed ports are arranged.The material that is shaped to sheet material adds via the conical entrance (on the right side of Fig. 8) that extends from right to left, and distributes up and down in two feed ports.These feed ports are described as extending to up and down the trilateral in two spaces, in the central row array structure of describing on the left side of Fig. 8.The left side of Fig. 8 shows the orthographic plan of many board molds.All digital units are mm.

Fig. 9: show the side elevational view (referring to following " embodiment-detection method-thermostability ") of the glass equipment be used to measure thermostability, have above two the hole and on the right side.All digital units are mm.

Embodiment

Other detection method

The detection of molar mass

The molar mass of polymkeric substance detects in SEC equipment by size exclusion chromatography.This SEC equipment is made up of the combination of following separator column: length is that 5cm and diameter are the elementary post of 7.5mm, and length is that 30cm and diameter are second linear columns of 7.5mm.Separate substance in two posts is the PL-HFIP gel, from Polymer Laborateries.Used detector comprises the differential refractometer from AgilentG1362A.The mixture of being made up of hexafluoroisopropanol and 0.05% trifluoroacetic acid potassium is used as eluent.Flow velocity is 0.5ml/ minute, and column temperature is 40 ℃.Be injected into the solution of 60 microlitres, its concentration is 1.5g sample/L eluent.This sample solution has used Millipor Millex GF (hole width is 0.2 micron) to filter in advance.Molar mass M be 505-2740000g/mol narrow distribution PMMA standard substance (from PSS, Mainz, DE) be used for the calibration.

Thermostability

WL N ₂: in nitrogen, be heated under 222 ℃ of situations of 2 hours the weight loss (WL) of the sample of forming by the 1.2g pellet.

WL air: in air, be heated under 222 ℃ of situations of 2 hours the weight loss (WL) of the sample of forming by the 1.2g pellet.For used equipment, referring to Fig. 9 with for the associated description of these figure.

When beginning WL detects, will be used for the balance taring of this purpose.In the double-walled container of being made up of two experiment tubes, the weight of weighing sample, tolerance range are 0.1mg, and one of them experiment tube is placed on (common experiment tube, 100x10mm among another experiment tube; The heavy wall experiment tube of special preparation, 100x12.5mm).

The thin copper cash of length for about 400mm is fixed on the upper limb of outer tube.This is used for double-walled container is suspended on particular device (participate in Fig. 9 and for the associated description of these figure).For detect WL in nitrogen, upper part of equipment is used and was adapted to particular atmosphere in 15 minutes, does not promptly have temperature to increase.Then these experiment tubes are reduced on the base, here kept 2 hours in 222 ℃.Nitrogen flow rate is 15l/h, detects each experiment tube under the help of Rota.

After 2 hours, under the help of copper cash, take out double-walled container in the slave unit, and in air, cooled off 20-25 minute.And then on balance, weigh, calculate WL according to following formula:

WL[%]-(loss x100/ initial weight).

Elastic tensile modulus

Elastic tensile modulus detects (23 ℃, 1mm/ minute) according to ISO 527

Yielding stress

Yielding stress detects (23 ℃, 50mm/ minute) according to ISO 527.

DSC, crystallization rate

Measure Tc T according to DIN EN 53765 _CPAnd crystallization rate.

Be used for component according to the embodiment of table 1-4

Component (A1)

Polyacetal copolymer is made up of the three _ alkane of 96.2 weight % and the butyleneglycol formal of 3.8 weight %.Product also contains the heat-labile fraction of unconverted three _ alkane and the 5 weight % of the 6-8 weight % that has an appointment.In case heat-labile fraction degraded, the melt volume speed of multipolymer is 7.5cm ³/ 10 minutes (190 ℃/2.16kg) according to ISO 1133.

Zeolitic material

B1:Purmol 4ST is from Zeochem AG, Uetikon, CH

B2:6278/03-48: Zn-MOF5, zinciferous porous crystalline material; Surface-area is 2380m ²/ g; Pore volume is 0.84ml/g; Mean pore size is 2.3nm

B3:Zeocat ZZ/0176, from Zeochem AG, Uetikon, CH, MFI structure, na form, Si: Al ratio=420,10-annular distance, bore dia: 0.55nm

B4:Zeocat Z6-02-03, from Zeochem AG, Uetikon, CH, FAU structure, na form, Si: Al ratio=2.75,12-annular distance, bore dia: 0.74nm

B5:Zeocat Z6-01-01, from Zeochem AG, Uetikon, CH, FAU structure, na form, Si: Al ratio=2.7-3,12-annular distance, bore dia: 0.74nm

B6:Zeocat PZ 2/25, from Zeochem AG, Uetikon, CH, MFI structure, na form, Si: Al ratio=12,10-annular distance, bore dia: 0.55nm

B7:Zeosorb 42; Explanation referring to Fig. 1

B8:Zeocat PZ 2/50, from Zeochem AG, Uetikon, CH, MFI structure, H form, Si: AI ratio=12,10-annular distance, bore dia: 0.55nm

B9:FM-8, from Zeochem AG, Uetikon, CH, MOR structure, na form, Si: Al ratio=6,12-annular distance, bore dia: 0.7nm

Component (C)

Talcum (Mikro-Talc I.T.Extra)

Particle diameter %

＜20 micron 100

＜10 micron 99

＜5 micron 85

＜3 micron 60

＜2 micron 43

Measure by analysis by sedimentation.

Component (D1)

Irganox_245 is from Ciba.

Component (D2)

Molar mass is the polyamide oligomer as well as of about 3000g/mol, pass through based on US3 by hexanolactam, hexamethylene-diamine, hexanodioic acid and propionic acid (as molecular weight regulator), the method of 960,984 embodiment 5-4 (" the two end-blockings of PA-") preparation: be to use propionic acid to replace acetate with the difference of this embodiment.

HMD: hexanodioic acid: hexanolactam: the mol ratio of propionic acid is 13.1: 1.02: 17: 4.2, and at US3, HMD among 960,984 the embodiment 5-4: hexanodioic acid: hexanolactam: the mol ratio of acetate is 13.1: 12.1: 13.6: 2.

High-load relatively propionic acid allows to reach the free amine group end group (US3, embodiment 5-4:62.5 equivalent/100 myriagrams of 960,984) of the 18-35meq/kg (mval/kg) of remarkable small proportion.

Component (D3)

Synthetic magnesium silicate (Ambosol_, PQ France) has following character:

The content of MgO 〉=14.8 weight %,

SiO ₂Content 〉=59 weight %,

SiO ₂: the MgO ratio is 2.7mol/mol

Tap density is 20-30g/100ml

Light loss＜25 weight %

Component (D4)

Loxiol_P1206 is from Cognis (Stearic diglyceride)

Be used for component according to the embodiment of table 5

Component (A1)

Polyacetal copolymer is made up of the three _ alkane of 96.2 weight % and the ethylene glycol acetal of 3.5 weight %.Product also contains the heat-labile fraction of unconverted three _ alkane and the 5 weight % of the 2-5 weight % that has an appointment.In case heat-labile fraction degraded, the melt volume speed of multipolymer is 7.5cm ³/ 10 minutes (190 ℃/2.16kg) according to ISO 1133.

Zeolitic material

B1:Purmol 4ST is from Zeochem AG, Uetikon, CH

Component (D1)

Irganox_245 is from Ciba.

Component (D2)

Polymeric amide Ultramid_C3101 is from BASF AG, Ludwigshafen.

Component (D4)

Loxiol_P1206 is from Cognis (Stearic diglyceride)

Component (D8)

White oil.

The preparation of moulding compound

In order to prepare moulding compound, component (A1) is being mixed with the component (Bi) of amount shown in the table, (C) with (Di) in the dry mixed device under 23 ℃ the temperature.The mixture of gained introduced have that (ZSK 30, from Werner﹠amp in the airy twin screw extruder; Pfieiderer), 230 ℃ of following homogenizing, and devolatilization, the mixture of homogenizing is extruded the die orifice by 2mm with the form of line material, and by the granulation of Scheer line material tablets press.The length of cylindrical pellets is 3mm, and diameter is 2.5mm.

Carry out the devolatilization in downstream then by the POM pellet of in tower dryer, handling 6kg, use the volumetric flow rate of 12l/h, and 50g (kg air) water vapour carried out 5 hours with reflux type at 145 ℃ of airflows with 0.6m/s.

Moulded product and experimental result

The component of moulded product and experimental result provide in table 1-5.

Table 1

Mix specification: the POM of every kg (=component (A1))

D1[weight %]	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500
									D2[weight %]	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400
D3[weight %]	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500
									D4[weight %]	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500
C[weight %]	?0.1250		?0.1250		?0.1250
									B1[weight %]		?0.100	?0.100	?0.200	?0.200	?0.250	?0.350	?0.400
At N 2In heat experiment (WL, %)	?0.09	?0.01	?0.02	?0.02	?0.01	?0.01	?0.01	?0.04
									Aerial heat experiment (WL, %)	?1.63	?1.30	?1.32	?1.24	?1.29	?1.40	?1.26	?1.34
?VDA275?[ppm]	?7	?4	?5	?3	?4	?2	?3	?3

Table 2

Mix specification: the POM of every kg (=component A)

D1[weight %]	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500	?0.3500
									D2[weight %]	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400	?0.0400
D3[weight %]	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500	?0.0500
									D4[weight %]	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500	?0.1500
C[weight %]	?0.1250	?0.1250	?0.1250	?0.1250	?0.1250	?0.1250	?0.1250	?0.1250
									B1[weight %]		?0.1
B2[weight %]			?0.1
									B3[weight %]				?0.1
B4[weight %]					?0.1
									B5[weight %]						?0.1
B6[weight %]							?0.1
									B7[weight %]								?0.1
At N 2In heat experiment (WL, %)	?0.17	?0.04	?0.50	?0.13	?0.62	?0.16	?0.17	?0.13
									Aerial heat experiment (WL, %)	?1.54	?1.38	?3.37	?1.40	?2.37	?1.41	?1.51	?1.33
?VDA275?[ppm]	?8	?5	?13	?9	?80	?18	?21	?10

Table 3

Mix specification: the POM of every kg (=component A)

D1[weight %]	?0.350	?0.350	?0.350	?0.350	?0.350	?0.350	?0.350
								D4[weight %]	?0.150	?0.150	?0.150	?0.150	?0.150	?0.150	?0.150
B3[weight %]		?0.1
								B1[weight %]			?0.1
B2[weight %]				?0.1
								B6[weight %]					?0.1
B8[weight %]						?0.1
								B9[weight %]							?0.1
?DSC(TcP)?[℃]	?138.9	?139.5	?139.4	?140.7	?139.1	?139.5	?1139.3
								Crystallization rate [minute]	?0.883	?0.843	?0.883	?0.607	?0.730	?0.773	?0.823
Elastic tensile modulus [MPa]	?2587	?2682	?2643	?2671	?2609	?2610	?2610
								Yielding stress [MPa]	?62.19	?63.95	?63.05	?63.76	?63.52	?62.63	?63.18

Detect the size of primary crystal

In order to detect the size of primary crystal, prepare the micro-photograph of SE (referring to Fig. 2-7) of material Purmol 4ST and Zeosorb 42 (on seeing).Select and detect 30 particles of every kind of material at random.Obtain the particle diameter that table 4 provides:

Table 4

The particle numbering	Purmol 4ST (length, micron)	Zeosorb 42 (length, micron)
			1	?2.70	?1.65
?2	?2.60	?1.68
			?3	?1.65	?1.53
?4	?2.34	?1.60
			?5	?2.59	?1.20
?6	?2.65	?1.60
			?7	?1.14	?1.68
?8	?1.69	?1.43
			?9	?2.79	?1.39
?10	?2.23	?1.31
			?11	?2.46	?1.12
?12	?2.19	?1.37
			?13	?2.28	?1.37
?14	?1.83	?0.97
			?15	?2.41	?1.36
?16	?1.94	?1.32
			?17	?2.42	?2.09
?18	?2.15	?1.31
			?19	?2.35	?0.84
?20	?2.88	?1.38
			?21	?2.78	?1.88
?22	?2.25	?1.65
			?23	?3.27	?1.19
?24	?2.56	?1.68
			?25	?1.84	?1.23
?26	?2.68	?1.01
			?27	?1.74	?1.94
?28	?2.54	?1.02
			?29	?1.47	?1.25
?30	?2.13	?1.70
			Mean value	?2.28	?1.42
Standard deviation	?0.47	?0.30

Table 5

A1[weight %]	?99.22
		D1[weight %]	?0.35
D2[weight %]	?0.04
		D4[weight %]	?0.15
D8[weight %]	?0.04
		B1[weight %]	?0.20
At N 2In heat experiment (WL, %)	?0.03
		Aerial heat experiment (WL, %)	?1.30
?VDA275[ppm]	?8
		Elastic tensile modulus [MPa]	?2431
Yielding stress [MPa]	?59.9

Claims (31)

1. moulding compound, its at least a polyoxymethylene that contains 10-99.999 weight % is as component (A1) with based at least a zeolitic material of the weight meter 0.001-10 weight % of the component that exists in the moulding compound (A1), the bore dia of described zeolitic material is determined in the scope of 0.3-0.5nm according to DIN66134 and DIN66135, and the particle diameter of wherein said zeolitic material is determined in the scope of 3-7 micron according to ISO13320.

2. moulding compound as claimed in claim 1, wherein the bore dia of zeolitic material is in the 0.37-0.43nm scope.

3. moulding compound as claimed in claim 1 or 2, wherein the particle diameter of zeolitic material is measured according to ISO13320 in the 4-6 micrometer range.

4. as each described moulding compound among the claim 1-3, it contains the zeolitic material of 0.05-0.50 weight %, based on the weight meter of the component that exists in moulding compound (A1).

5. as each described moulding compound among the claim 1-4, wherein according to SiO ₂: Al ₂O ₃Mol ratio calculate the Si of described zeolitic material: the Al mol ratio is in being up to 5: 1 scope.

6. as each described moulding compound among the claim 1-5, wherein at least 90% of the primary crystal size of zeolitic material is in the scope of 1.5-3.0 micron, measures by SEM.

7. as each described moulding compound among the claim 1-6, wherein the zeolitic material of at least 75 weight % is not to exist with the H form.

8. as each described moulding compound among the claim 1-7, wherein according to SiO ₂: Al ₂O ₃Mol ratio is calculated, the Si of zeolitic material: the Al mol ratio is 1: 1 to 2: 1, measure by SEM zeolitic material the primary crystal size at least 95% be in the scope of 1.75-2.75 micron, and the described zeolitic material of at least 95 weight % is not to exist with the H form.

9. as each described moulding compound among the claim 1-8, wherein said moulding compound does not comprise the spiro-compounds with at least one triazine ring.

10. as each described moulding compound among the claim 1-9, wherein said moulding compound does not comprise the organic compound that has single dispersion molar mass distribution and contain at least one primary amino and/or at least one secondary amino group.

11. as each described moulding compound among the claim 1-10, wherein said moulding compound also contains stablizer based on component (A1) weight meter 0.005-2 weight % as component (D1).

12. moulding compound as claimed in claim 11, wherein component (D1) is a sterically hindered phenol, and the weight ratio of sterically hindered phenol and zeolitic material is 7: 1 to 1: 2.

13. as each described moulding compound among the claim 1-12, it also contains at least a polymeric amide based on component (A1) weight meter 0.001-2 weight % as component (D2).

14. as each described moulding compound among the claim 1-13, it also contains based on the alkaline earth metal silicate of component (A1) weight meter 0.002-2 weight % and/or alkaline-earth metal glycerophosphate as component (D3).

15. as each described moulding compound among the claim 1-14, it also contains based on the following material of component (A1) weight meter 0.01-5 weight % as component (D4):

-at least a saturated or unsaturated aliphatic carboxylic acid and at least a polyvalent alcohol or the ester that obtains with at least a radical of saturated aliphatic alcohol reaction that can be by at least a 10-40 of a having carbon atom with 2-40 carbon atom,

The acid amides of-at least a saturated or unsaturated aliphatic carboxylic acid and amine reaction acquisition that can be by at least a 10-40 of a having carbon atom with 2-20 carbon atom,

-at least a the ether that can pass through at least a alcohol and the acquisition of at least a reacting ethylene oxide.

16. as each described moulding compound among the claim 1-15, it also contains talcum based on component (A1) weight meter 0.01-5 weight % as component (C).

17. as each described moulding compound among the claim 1-16, it also contains white oil based on component (A1) weight meter 0.01-5 weight % as component (D8).

18. as each described moulding compound among the claim 1-17, wherein at least a polyoxymethylene is at least a POM-H Acetal homopolymer or at least a polyacetal copolymer, or the mixture of being made up of at least a POM-H Acetal homopolymer and at least a polyacetal copolymer.

19. as each described moulding compound among the claim 1-18, its at least a urethane that also contains maximum 55 weight % is as component (A2), based on the weight meter of component (A1).

20. moulding compound as claimed in claim 19, wherein said urethane are the thermoplastic poly ester polyurethanes, measure according to DIN53505, the Xiao A hardness of described thermoplastic poly ester polyurethane is 75-90.

21. as each described moulding compound among the claim 1-20, the burst size of methanal of described moulding compound is 8ppm at the most, preferably 7ppm at the most measures according to VDA275.

22. zeolitic material as the purposes of the component in the moulding compound that contains at least a polyoxymethylene, is used to reduce the burst size of methanal of described moulding compound.

23. purposes as claimed in claim 22, the bore dia of wherein said zeolitic material is determined in the 0.3-0.5nm scope according to DIN66134 and DIN66135.

24. as claim 22 or 23 described purposes, the particle diameter of wherein said zeolitic material is determined in the 3-7 micrometer range according to ISO13320.

25. as each described purposes among the claim 22-24, be used for the burst size of methanal of described moulding compound is reduced to 8ppm at the most, preferably 7ppm at the most measures by VDA275.

26. as each described purposes among the claim 22-25, wherein have single disperse molar mass and have primary amine groups and/or the organic compound of secondary amine as the component of the burst size of methanal that is used to reduce described moulding compound in the moulding compound.

27. method for preparing as each described moulding compound among the claim 1-21, comprise at least a polyoxymethylene is mixed with zeolitic material, the bore dia of described zeolitic material is determined in the scope of 0.3-0.5nm according to DIN66134 and DIN66135 and the particle diameter of described zeolitic material is determined in the scope of 3-7 micron according to ISO13320.

28. method as claimed in claim 27 comprises the composition that contains polyoxymethylene and zeolitic material is extruded under 100-270 ℃ temperature.

29., also comprise described moulding compound processing is obtained moulded product as claim 27 or 28 described methods.

30. a moulded product, it obtains by method as claimed in claim 29, and its burst size of methanal is 8ppm at the most, and preferably 7ppm at the most measures according to VDA275.

31. maybe can be used to prepare the purposes of moulded product as each described moulding compound among the claim 1-21 by the moulding compound that method as described in claim 27 or 28 obtains, wherein said moulded product is toy or toy part, or car accessories, aircraft accessory or ship's fitments, or the parts of car accessories, the parts of aircraft accessory or the parts of ship's fitments, or the parts of packing or packing, or the parts of container or container, or the parts of housed device or housed device, or the parts of medical facilities or medical facilities, or the component of toiletry, or the parts of electronics or electric installation, or in building construction used equipment or the parts of this equipment.

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